Gas sensor

• US 6,303,011 B1
• Filed: 06/18/1998
• Issued: 10/16/2001
• Est. Priority Date: 06/23/1997
• Status: Expired due to Fees

• Current Assignee: Kabushiki Kaisha Riken
• Original Assignee: Kabushiki Kaisha Riken
• Inventors: Ono, Takashi, Kunimoto, Akira, Gao, Yunzhi, Yan, Yongtie, Hasei, Masaharu, Nakanouchi, Yukio
• Primary Examiner(s): Warden, Sr., Robert J.
• Assistant Examiner(s): Olsen, Kaj K.
• Application Number:
  US09/099,401
• Time in Patent Office: 1,216 Days
• Field of Search: 204/426, 204/424, 204/425, 204/427, 205/781
• US Class Current: 204/425
• CPC Class Codes: G01N 27/4074 for detection of gases other than oxygen
• CPC Class Codes: G01N 27/4075 Composition or fabrication of the electrodes and coatings thereon, e.g. catalysts
• CPC Class Codes: G01N 33/0037 for NOx
• CPC Class Codes: Y02A 50/20 Air quality improvement or preservation, e.g. vehicle emission control or emission reduction by using catalytic converters

Abstract

A nitrogen oxide sensor includes a solid electrolytic substrate exhibiting oxygen ion conductivity, a noble-metal reference electrode, which is active only to oxygen, formed on one side of the solid electrolytic substrate, and a sensing electrode, which is active to NOx and oxygen, formed on the opposite side of the solid electrolytic substrate. A potential difference across the sensing electrode and the reference electrode is output as a signal indicative of NOx concentration. Nitrogen oxides in a gas to be examined or measured gas are converted to NO₂ and to peroxides of nitrogen such as N₂O₅ and NO₃, after which the nitrogen oxides in the gas to be examined or measured gas are sensed by the sensing electrode as the peroxides of nitrogen such as N₂O₅ and NO₃ or as a mixed gas of NO₂ and the peroxides of nitrogen.

Claims

1. A nitrogen oxide sensor comprising:

first and second solid electrolytic substrates exhibiting oxygen ion conductivity and defining a measurement chamber;

a noble-metal reference electrode, which is active only to oxygen, formed on one side of said first solid electrolytic substrate;

an NOx sensing electrode, which is at least active to NOx and oxygen, formed on the opposite side of said first solid electrolytic substrate within said measurement chamber, a potential difference across said sensing electrode and said reference electrode being output as a signal indicative of NOx concentration; and

means for converting nitrogen oxides in a gas to be examined or measured gas to NO₂ and to peroxides of nitrogen and formed within said measurement chamber, after which the nitrogen oxides in the gas to be examined or measured gas are sensed by said sensing electrode as the peroxides of nitrogen or as a mixed gas of NO₂ and said peroxides of nitrogen.

2. The sensor according to claim 1, wherein the means for converting nitrogen oxides comprises an NOx converting electrode formed within said measurement chamber on said second solid electrolytic substrate, said NOx converting electrode having the ability to oxidize nitrogen oxides in the gas to be examined or measured gas to NO₂ and peroxide compounds of nitrogen having an oxidation order greater than that of NO₂, said sensor further comprising a counter electrode of said NOx converting electrode opposed to said NOx converting electrode through said second solid electrolytic substrate, wherein the nitrogen oxides in the gas to be examined or measured gas are converted to NO₂ and to peroxides of nitrogen by said NOx converting electrode.

3. The sensor according to claim 2, further comprising an oxygen sensing electrode disposed in said measurement chamber and an oxygen pumping electrode disposed in said measurement chamber for adjusting oxygen concentration, wherein a current applied to said oxygen pumping electrode is controlled using an output signal from said oxygen sensing electrode.

4. The sensor according to claim 3, wherein a porous protective film having heat resistance and an oxidation catalyst ability is formed at least on the NOx sensing electrode or the oxygen pumping electrode and the NOx sensing electrode.

5. The sensor according to claim 3, further comprising an auxiliary pumping portion for controlling oxygen concentration at said NOx sensing electrode;

and wherein a driving voltage applied to said auxiliary pumping portion is controlled based upon the oxygen concentration sensed by said oxygen sensing electrode.

6. The sensor according to claim 5, wherein an oxidation catalyst for oxidizing nitrogen oxide gases is formed between said oxygen pumping electrode and said NOx sensing electrode.

7. The sensor according to claim 5, wherein (1) (a) one of the oxygen pumping electrode or an electrode of the auxiliary oxygen pumping portion and (b) the NOx sensing electrode or (2) both the Nox sensing electrode and said reference electrode are disposed in said measurement chamber, and a gas diffusion inlet is provided in said chamber.

8. The sensor according to claim 7, wherein said oxygen pumping electrode and at least the NOx sensing electrode are disposed with their electrode surfaces opposing each other in the chamber.

9. The sensor according to claim 8, wherein a space between said oxygen pumping electrode and at least the NOx sensing electrode is filled with a porous body.

10. The sensor according to claim 9, wherein the porous body filling the space between said oxygen pumping electrode and at least the NOx sensing electrode has a high degree of electrical insulation.

11. The sensor according to claim 1, further comprising a heater provided on at least one of said first and second solid electrolytic substrates for controlling the temperature of said sensor.

12. The sensor according to claim 11, wherein the NOx sensing electrode produces a mixed potential owing to concurrent electrochemical reactions with oxygen and NOx at the NOx sensing electrode, and a potential difference based upon total NOx gas concentration between the NOx sensing electrode and its counter electrode is measured.

13. The sensor according to claim 1, wherein said NOx sensing electrode is an alloy electrode comprising platinum and rhodium or is a cermet electrode comprising a platinum-rhodium alloy and zirconia.