CO gas sensor and method of using same

• US 6,488,836 B1
• Filed: 07/26/2000
• Issued: 12/03/2002
• Est. Priority Date: 07/29/1999
• Status: Expired due to Term

• Current Assignee: Kabushikikaisha Equos Research
• Original Assignee: Kabushikikaisha Equos Research
• Inventors: Kunimatsu, Keiji, Akita, Hidemi, Saguchi, Katsuhiko, Nakata, Toshihide
• Primary Examiner(s): TUNG, TA HSUNG
• Application Number:
  US09/625,729
• Time in Patent Office: 860 Days
• Field of Search: 204/421-429, 429/90, 429/12, 205/783.5, 205/784, 205/784.5, 205/785
• US Class Current: 205/784
• CPC Class Codes: G01N 27/4074 for detection of gases other than oxygen
• CPC Class Codes: G01N 33/004 for CO, CO2
• CPC Class Codes: H01M 8/04089 of gaseous reactants
• CPC Class Codes: Y02E 60/50 Fuel cells

Abstract

A CO gas sensor is equipped with a detecting unit in which a solid electrolyte membrane is held between a detection electrode and a counter electrode, and a voltage applying unit which applies voltage between the detection electrode and the counter electrode and changes the voltage. The detection electrode includes an electrochemically active first catalyst in an electrically conductive porous body, a reaction layer having a density of 1 ng/cm²-100 μg/cm² and having a thickness of 0.3 nm-15 μm, and the counter electrode includes an electrochemically active second catalyst carried on an electrically conductive porous body.

Claims

1. A CO gas sensor for measuring CO concentration in an atmosphere containing CO and hydrogen gases, said sensor comprising:

a detector including a detection electrode, a counter electrode and a solid electrolyte member sandwiched between said detection electrode and said counter electrode, wherein said detection electrode comprises a first electrochemically active catalyst carried on an electrically conductive porous body and forming a reaction layer thereon, said first catalyst having a density of 1 ng/cm²-100 μ

g/cm² and a thickness of 0.3 nm-15 μ

m, and wherein said counter electrode comprises a second electrochemically active catalyst carried on an electrically conductive porous body;

means for contacting said detector with the atmosphere;

voltage application means for applying, between said detection electrode and said counter electrode while in contact with the atmosphere, a voltage in a wave form wherein the voltage continuously cycles between CO oxidation potential and CO adsorption potential and for thereby causing a response current to flow between said electrodes responsive to the applied voltage;

means for measuring the amount of response current; and

determination means for determining the CO concentration based on the measured amount of response current.

2. The CO gas sensor according to claim 1, wherein the first catalyst and the second catalyst are each a metal selected from the group consisting of Pt, Au, Cu, Ni, Pd, Ag, Rh, Ru and alloys of said metals.

3. The CO gas sensor according to claim 1, wherein the first catalyst comprises Pt and the second catalyst comprises Pt-Ru.

4. The CO gas sensor according to claim 1, wherein a second reaction layer comprising the second catalyst is formed on the porous body of the counter electrode and a total weight of the second catalyst in the second reaction layer is 10-1000-fold of total weight of the first catalyst in the reaction layer of the detection electrode.

5. The CO gas sensor according to claim 1, wherein said counter electrode has an electrochemically active area 10-1000-fold of an electrochemically active area of the detection electrode.

6. The CO gas sensor according to claim 1, wherein the body of the detection electrode has a void rate of 10-90% and an average void diameter of 1 nm-100 μ

m.

7. The CO gas sensor according to claim 1, further comprising a diffusion controlling membrane disposed on the detection electrode.

8. A fuel cell apparatus equipped with the CO gas sensor according to claim 1.

9. The CO gas sensor according to claim 1 wherein said determination means determines the CO concentration based on rate of decrease in the measured amount of response current.

10. The CO gas sensor according to claim 1 wherein said voltage application means comprises a direct current voltage source and a voltage changing circuit.

11. A CO gas sensor for measuring CO concentration in an atmosphere containing CO and hydrogen gases, said sensor comprising:

a detector including a detection electrode, a counter electrode and a solid electrolyte member sandwiched between said detection electrode and said counter electrode;

means for contacting said detector with the atmosphere;

voltage application means for applying, between said detection electrode and said counter electrode while in contact with the atmosphere, a voltage in a wave form wherein the voltage continuously cycles between CO oxidation potential and CO adsorption potential and for thereby causing a response current to flow between said electrodes responsive to the applied voltage, said response current being 0.001 mA/cm² to 1 A/cm² at said CO adsorption potential;

means for measuring the amount of response current; and

determination means for determining the CO concentration based on the measured amount of response current.

12. The CO gas sensor according to claim 11, wherein said response current is 0.01 mA/cm²-0.1 A/cm² at the CO adsorption potential.

13. The CO gas sensor according to claim 11, wherein said response current is 0.1 mA/cm²-0.01 A/cm² at the CO adsorption potential.

14. A fuel cell apparatus equipped with the CO gas sensor according to claim 11.

15. The CO gas sensor according to claim 11 wherein said determination means determines the CO concentration based on rate of decrease in the measured amount of response current.

16. The CO gas sensor according to claim 11 wherein said voltage application means comprises a direct current voltage source and a voltage changing circuit.

17. A CO gas sensor for measuring CO concentration in an atmosphere containing CO and hydrogen gases, said sensor comprising:

a detector including a detection electrode, a counter electrode and a solid electrolyte member sandwiched between said detection electrode and said counter electrode, wherein the detection electrode comprises a porous body which is electrochemically inactive and has electrical conductivity, and a reaction layer which is formed on the body and contains an electrochemically active first material, wherein density of the reaction layer is 1 ng/cm²-100 μ

g/cm² and thickness of the reaction layer is 0.3 nm-15 μ

m;

means for contacting said detector with the atmosphere;

voltage application means for applying, between said detection electrode and said counter electrode while in contact with the atmosphere, a voltage in a wave form wherein the voltage continuously cycles between CO oxidation potential and CO adsorption potential and for thereby causing a response current to flow between said electrodes responsive to the applied voltage;

means for measuring the amount of response current; and

determination means for determining the CO concentration based on the measured amount of response current.

18. A method for measuring CO concentration in an atmosphere containing CO and hydrogen gases, said method comprising:

providing a detector including a detection electrode, a counter electrode and a solid electrolyte membrane sandwiched between said detection electrode and said counter electrode;

contacting the detector with the atmosphere;

applying a voltage between said electrodes while in contact with the atmosphere, said voltage continuously alternating between a CO oxidation potential upper limit and a CO adsorption potential lower limit, thereby causing a response current to flow between the electrodes responsive to the applied voltage;

determining the rate of current decrease in transition from the CO oxidation potential to the CO adsorption potential; and

determining CO concentration based on the determined rate of current decrease.