Electrochemical cells and methods using perovskites

• US 5,643,429 A
• Filed: 02/02/1995
• Issued: 07/01/1997
• Est. Priority Date: 03/09/1994
• Status: Expired due to Term

• Current Assignee: Gas Technology Institute
• Original Assignee: Gas Research Institute (GTI Energy)
• Inventors: Wachsman, Eric David
• Primary Examiner(s): Bell, Bruce F.
• Application Number:
  US08/382,667
• Time in Patent Office: 880 Days
• Field of Search: 204/424, 204/425, 204/426, 204/427, 204/428, 204/429, 204/421, 204/412, 204/153.16, 204/153.14, 204/153.17, 204/153.18, 204/409
• US Class Current: 205/781
• CPC Class Codes: G01N 27/4074 for detection of gases other than oxygen
• CPC Class Codes: G01N 33/0031 comprising two or more sensors, e.g. a sensor array electrochemical electrode arrays G01N27/27
• 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

Sensors (10, 40) accurately measure the concentration of an oxide compound, such as nitrogen oxide NO_x, in a gas mixture (11) which can include oxygen O₂. The sensors (10, 40) each comprise a chamber (12, 42) adapted to receive the gas mixture (11) as well as first and second electrochemical cells (16, 17) for consuming oxygen and/or the oxide compound in the chamber (12, 42). The first electrochemical cell (16) comprises a first internal electrode (16a) inside the chamber (12, 42), a first external electrode (16b) outside the chamber (12, 42), and a first electrolyte body (14'"'"') therebetween. The second electrochemical cell (17) comprises a second internal electrode (17a) inside the chamber (12, 42), a second external electrode (17b) outside the chamber (12, 42), and a second electrolyte body (14") therebetween. The first and second electrolyte bodies (14'"'"', 14") are permeable to oxygen ions. Significantly, the first and second internal electrodes (16a, 17a) are metal oxides having a perovskite lattice structure, which generally exhibit high relative selectivity between oxide compounds, including NO_x, and O₂. The electrical characteristics of the first and second electrochemical cells (16, 17) are manipulated and/or monitored in order to determine the concentration of NO_x within the chambers (12, 42) and the gas mixture (11).

Claims

1. An electrochemical cell for a sensor for enabling accurate measurement of an oxygen concentration in a gas mixture, comprising:

a first electrode to be exposed to said gas mixture, said first electrode having a perovskite that discriminates between oxygen and a variety of oxide compounds in said gas mixture, wherein said perovskite selectively reduces said oxygen in said gas mixture without reducing said oxide compounds;

a second electrode; and

an electrolyte interposed between said first and second electrodes for conducting ions when an electrical bias is imposed across said first and second electrodes;

wherein an electrical characteristic measured from said first and second electrodes exhibits a higher correspondence to said reduced oxygen than to said reduced oxide compounds.

2. The cell of claim 1, further comprising a housing defining an internal chamber, said cell residing within said chamber, said housing comprising an aperture in the shape of a pin through which said gas mixture can enter said chamber.

3. The cell of claim 1, further comprising a housing defining an internal chamber in the shape of a tube, said cell residing within said chamber, said chamber having first and second apertures for receiving and expelling said gas mixture respectively.

4. The cell of claim 1, wherein said electrolyte comprises zirconia.

5. The cell of claim 1, wherein said perovskite is selected from the group consisting of La₂ CuO₄, LaNiO₃, LaFeO₃, LaCoO₃, LaMnO₃, and LaSrCoO₃.

6. An electrochemical cell for a sensor for enabling accurate measurement of a concentration of an oxide compound in a gas mixture, comprising:

a first electrode to be exposed to said gas mixture, said first electrode having a perovskite that discriminates between said oxide compound and oxygen in said gas mixture, wherein said perovskite selectively reduces said oxide compound in said gas mixture without reducing said oxygen;

a second electrode; and

an electrolyte interposed between said first and second electrodes, said electrolyte for conducting ions when an electrical bias is imposed across said first and second electrodes;

wherein an electrical characteristic measured from said first and second electrodes exhibits a higher correspondence to said reduced oxide compound than to said reduced oxygen.

7. The cell of claim 6, further comprising a housing with an internal chamber, said cell residing within said chamber, said housing comprising an aperture in the shape of a pin through which said gas mixture can enter said chamber.

8. The cell of claim 6, further comprising a housing defining an elongated internal chamber in the shape of tube, said cell residing within said chamber, said chamber having first and second apertures for receiving and expelling said gas mixture respectively.

9. The cell of claim 6, wherein said electrolyte comprises zirconia.

10. The cell of claim 6, wherein said perovskite is selected from the group consisting of LaRuO₃, LaMnO₃, Pt, and Rh.

12. The cell of any one of claims 6 through 11, wherein said reduced oxide compound in said gas mixture is nitrogen oxide (NO_x).

11. An electrochemical cell for a sensor for enabling accurate measurement of a concentration of an oxide compound in a gas mixture, comprising:

a first electrode to be exposed to said gas mixture;

a second electrode; and

an electrolyte interposed between said first and second electrodes, said electrolyte for conducting ions when an electrical bias is imposed across said first and second electrodes;

wherein said first electrode has a perovskite having selectivity to reduce said oxide compound in said gas mixture so that an electrical characteristic associated with said electrodes exhibits a higher correspondence to a reduction in said oxide compound than any other reduction associated with any oxygen in said gas mixture.

13. A method for accurately measuring oxygen concentration in a gas mixture, comprising the steps of:

providing an electrochemical cell having first and second electrodes, said first electrode comprising a perovskite that discriminates between oxygen and oxide compounds in said gas mixture;

exposing said first electrode to said gas mixture wherein said perovskite selectively reduces said oxygen in said gas mixture without reducing said oxide compound; and

generating an electrical characteristic from said electrodes which exhibits a higher correspondence to said reduced oxygen than to said reduced oxide compound which corresponds to said oxygen concentration.

14. A method for accurately measuring oxide compound concentration in a gas mixture, comprising the steps of:

providing an electrochemical cell having first and second electrodes, said first electrode comprising a perovskite that discriminates between said oxide compounds and oxygen in said gas mixture;

exposing said first electrode to said gas mixture wherein said perovskite selectively reduces said oxide compound in said gas mixture without reducing said oxygen; and

generating an electrical characteristic from said electrodes which exhibits a higher correspondence to said reduced oxide compound than to said reduced oxygen and which corresponds to said oxide compound concentration.

15. The method of claim 14, wherein said oxide compound is nitrogen oxide (NO_x).