Login| Sign Up| Help| Contact|

Patent Searching and Data


Title:
HYDROGEN CONCENTRATION SENSOR
Document Type and Number:
WIPO Patent Application WO/2020/106442
Kind Code:
A1
Abstract:
An illustrative example hydrogen concentration sensor includes a hydrogen chamber configured to isolate hydrogen within the hydrogen chamber from gas outside the hydrogen chamber. A hydrogen evolving electrode is configured to generate pure hydrogen within the hydrogen chamber. A reference electrode is situated to be exposed to pure hydrogen within the hydrogen chamber. A detection electrode associated with the reference electrode is situated to be exposed to gas outside the hydrogen chamber. The detection electrode is configured to provide an indication of a concentration of hydrogen in the gas outside the hydrogen chamber.

Inventors:
PRESTON JOSHUA (US)
PATTERSON JR (US)
Application Number:
PCT/US2019/059768
Publication Date:
May 28, 2020
Filing Date:
November 05, 2019
Export Citation:
Click for automatic bibliography generation   Help
Assignee:
DOOSAN FUEL CELL AMERICA INC (US)
International Classes:
G01N27/00; G01N27/406; G01N27/416
Domestic Patent References:
WO2018209082A12018-11-15
Foreign References:
JP2000131273A2000-05-12
JP2005332610A2005-12-02
JP2015144092A2015-08-06
Attorney, Agent or Firm:
GASKEY, David J. (US)
Download PDF:
Claims:
CLAIMS

We claim:

1. A hydrogen concentration sensor, comprising:

a hydrogen chamber configured to isolate hydrogen within the hydrogen chamber from gas outside the hydrogen chamber;

a hydrogen evolving electrode configured to generate pure hydrogen within the hydrogen chamber;

a reference electrode situated to be exposed to pure hydrogen within the hydrogen chamber; and

a detection electrode associated with the reference electrode, the detection electrode being situated to be exposed to gas outside the hydrogen chamber, the detection electrode being configured to provide an indication of a concentration of hydrogen in the gas outside the hydrogen chamber.

2. The hydrogen concentration sensor of claim 1, wherein the hydrogen evolving electrode introduces a positive pressure within the hydrogen chamber.

3. The hydrogen concentration sensor of claim 2, wherein

the hydrogen chamber includes a vent; and

the positive pressure within the hydrogen chamber prevents the gas outside the hydrogen chamber from entering the hydrogen chamber through the vent.

4. The hydrogen concentration sensor of claim 1, wherein

the hydrogen evolving electrode is part of a first electrochemical cell; and

the reference electrode and the detection electrode are part of a second electrochemical cell.

5. The hydrogen concentration sensor of claim 4, wherein

the first electrochemical cell comprises a first matrix containing an electrolyte;

the first electrochemical cell comprises a hydrogen oxidizing electrode;

the first matrix is at least partially situated between the hydrogen oxidizing electrode and the hydrogen evolving electrode; and

a voltage is applied across the hydrogen evolving electrode and the hydrogen oxidizing electrode.

6. The hydrogen concentration sensor of claim 5, wherein the electrolyte in the first matrix comprises phosphoric acid.

7. The hydrogen concentration sensor of claim 4, wherein

the second electrochemical cell includes a second matrix at least partially situated between the reference electrode and the detection electrode; and

a voltage across the reference electrode and the detection electrode provides the indication of the concentration of hydrogen in the gas outside the hydrogen chamber.

8. The hydrogen concentration sensor of claim 7, wherein the second matrix contains phosphoric acid.

9. The hydrogen concentration sensor of claim 1, wherein positive pressure within the hydrogen chamber prevents the gas outside the hydrogen chamber from entering the hydrogen chamber.

10. The hydrogen concentration sensor of claim 1, wherein no current passes at the reference electrode.

11. A method of determining a concentration of hydrogen in a gas, the method comprising:

evolving pure hydrogen from the gas using a hydrogen evolving electrode;

at least temporarily containing the evolved pure hydrogen in a hydrogen chamber; exposing a reference electrode to the pure hydrogen in the hydrogen chamber;

exposing a detection electrode to the gas; and

determining a voltage across the reference electrode and the detection electrode as an indication of the concentration of hydrogen in the gas.

12. The method of claim 11, wherein the hydrogen evolving electrode is associated with a hydrogen oxidizing electrode and the method comprises

exposing a hydrogen oxidizing electrode to the gas; and

applying a voltage across the hydrogen oxidizing electrode and the hydrogen evolving electrode.

13. The method of claim 11, comprising

introducing a positive pressure within the hydrogen chamber; and

isolating the pure hydrogen in the hydrogen chamber from the gas using the positive pressure.

14. The method of claim 13, wherein the hydrogen evolving electrode introduces the positive pressure within the hydrogen chamber.

15. The method of claim 13, wherein

the hydrogen chamber includes a vent; and

the positive pressure within the hydrogen chamber prevents the gas outside the hydrogen chamber from entering the hydrogen chamber through the vent.

16. The method of claim 11 , wherein

the hydrogen evolving electrode is part of a first electrochemical cell; and

the first electrochemical cell comprises a first matrix containing an electrolyte;

the first electrochemical cell comprises a hydrogen oxidizing electrode;

the first matrix is at least partially situated between the hydrogen oxidizing electrode and the hydrogen evolving electrode; and

the method comprises applying a voltage across the hydrogen evolving electrode and the hydrogen oxidizing electrode.

17. The method of claim 16, wherein

the reference electrode and the detection electrode are part of a second electrochemical cell;

the second electrochemical cell includes a second matrix at least partially situated between the reference electrode and the detection electrode; and

the second matrix contains phosphoric acid.

18. The method of claim 11, wherein the gas is in a fuel cell power plant reformer and the method comprises

determining an operating condition of the reformer based on the determined concentration of hydrogen in the gas; and

adjusting operation of the reformer based on the operating condition.

19. The method of claim 18, wherein determining the operating condition and adjusting the operation are performed independent of determining a temperature in the reformer.

Description:
HYDROGEN CONCENTRATION SENSOR

CROSS REFERENCE TO RELATED APPLICATION

[oooi] This application claims priority to US Patent Application No. 16/198,044, which was filed on November 21, 2018.

BACKGROUND

[0002] Various devices and processes depend on hydrogen for proper operation. For example, fuel cells typically use hydrogen as a reactant fuel in an electrochemical process to generate electricity. Inadequate hydrogen concentration in the reactant fuel results in unsatisfactory fuel cell performance.

[0003] Hydrogen concentration sensors for fuel cells are known. Some such sensors rely on the Nernst Potential across two electrodes induced by a difference in hydrogen concentration at the respective electrodes. One shortcoming of that type of hydrogen sensor is that a reference electrode generates pure hydrogen as electrical current is applied to the reference electrode. Using the reference electrode to evolve pure hydrogen in this way tends to introduce potential shifts at the reference electrode, which interferes with accurate hydrogen concentration measurement.

SUMMARY

[0004] An illustrative example hydrogen concentration sensor includes a hydrogen chamber configured to isolate hydrogen within the hydrogen chamber from gas outside the hydrogen chamber. A hydrogen evolving electrode is configured to generate pure hydrogen within the hydrogen chamber. A reference electrode is situated to be exposed to pure hydrogen within the hydrogen chamber. A detection electrode associated with the reference electrode is situated to be exposed to gas outside the hydrogen chamber. The detection electrode is configured to provide an indication of a concentration of hydrogen in the gas outside the hydrogen chamber.

[0005] In an example embodiment having one or more features of the hydrogen concentration sensor of the previous paragraph, the hydrogen evolving electrode introduces a positive pressure within the hydrogen chamber. [0006] In an example embodiment having one or more features of the hydrogen concentration sensor of any of the previous paragraphs, the hydrogen chamber includes a vent. The positive pressure within the hydrogen chamber prevents the gas outside the hydrogen chamber from entering the hydrogen chamber through the vent.

[0007] In an example embodiment having one or more features of the hydrogen concentration sensor of any of the previous paragraphs, the hydrogen evolving electrode is part of a first electrochemical cell and the reference electrode and the detection electrode are part of a second electrochemical cell.

[0008] In an example embodiment having one or more features of the hydrogen concentration sensor of any of the previous paragraphs, the first electrochemical cell comprises a first matrix containing an electrolyte. The first electrochemical cell comprises a hydrogen oxidizing electrode. The first matrix is at least partially situated between the hydrogen oxidizing electrode and the hydrogen evolving electrode. A voltage is applied across the hydrogen evolving electrode and the hydrogen oxidizing electrode.

[0009] In an example embodiment having one or more features of the hydrogen concentration sensor of any of the previous paragraphs, the electrolyte in the first matrix comprises phosphoric acid.

[oooio] In an example embodiment having one or more features of the hydrogen concentration sensor of any of the previous paragraphs, the second electrochemical cell includes a second matrix at least partially situated between the reference electrode and the detection electrode. A voltage across the reference electrode and the detection electrode provides the indication of the concentration of hydrogen in the gas outside the hydrogen chamber.

[oooii] In an example embodiment having one or more features of the hydrogen concentration sensor of any of the previous paragraphs, the second matrix contains phosphoric acid.

[00012] In an example embodiment having one or more features of the hydrogen concentration sensor of any of the previous paragraphs, positive pressure within the hydrogen chamber prevents the gas outside the hydrogen chamber from entering the hydrogen chamber. [00013] In an example embodiment having one or more features of the hydrogen concentration sensor of any of the previous paragraphs, no current passes at the reference electrode.

[00014] An illustrative example method of determining a concentration of hydrogen in a gas includes evolving pure hydrogen from the gas using a hydrogen evolving electrode, at least temporarily containing the evolved pure hydrogen in a hydrogen chamber, exposing a reference electrode to the pure hydrogen in the hydrogen chamber, exposing a detection electrode to the gas, and determining a voltage across the reference electrode and the detection electrode as an indication of the concentration of hydrogen in the gas.

[00015] In an example embodiment having one or more features of the method of the previous paragraphs, the hydrogen evolving electrode is associated with a hydrogen oxidizing electrode and the method comprises exposing a hydrogen oxidizing electrode to the gas and applying a voltage across the hydrogen oxidizing electrode and the hydrogen evolving electrode.

[00016] In an example embodiment having one or more features of the method of any of the previous paragraphs, the method includes introducing a positive pressure within the hydrogen chamber and isolating the pure hydrogen in the hydrogen chamber from the gas using the positive pressure.

[00017] In an example embodiment having one or more features of the method of any of the previous paragraphs, the hydrogen evolving electrode introduces the positive pressure within the hydrogen chamber.

[00018] In an example embodiment having one or more features of the method of any of the previous paragraphs, the hydrogen chamber includes a vent. The positive pressure within the hydrogen chamber prevents the gas outside the hydrogen chamber from entering the hydrogen chamber through the vent.

[00019] In an example embodiment having one or more features of the method of any of the previous paragraphs, the hydrogen evolving electrode is part of a first electrochemical cell. The first electrochemical cell comprises a first matrix containing an electrolyte. The first electrochemical cell comprises a hydrogen oxidizing electrode. The first matrix is at least partially situated between the hydrogen oxidizing electrode and the hydrogen evolving electrode. The method comprises applying a voltage across the hydrogen evolving electrode and the hydrogen oxidizing electrode. [00020] In an example embodiment having one or more features of the method of any of the previous paragraphs, the reference electrode and the detection electrode are part of a second electrochemical cell. The second electrochemical cell includes a second matrix at least partially situated between the reference electrode and the detection electrode. The second matrix contains phosphoric acid.

[00021] In an example embodiment having one or more features of the method of any of the previous paragraphs, the gas is in a fuel cell power plant reformer and the method comprises determining an operating condition of the reformer based on the determined concentration of hydrogen in the gas and adjusting operation of the reformer based on the operating condition.

[00022] In an example embodiment having one or more features of the method of any of the previous paragraphs, determining the operating condition and adjusting the operation are performed independent of determining a temperature in the reformer.

[00023] Various features and advantages of at least one disclosed example embodiment will become apparent to those skilled in the art from the following detailed description. The drawings that accompany the detailed description can be briefly described as follows.

BRIEF DESCRIPTION OF THE DRAWINGS

[00024] Figure 1 schematically illustrates an example hydrogen concentration sensor designed according to an embodiment of this invention.

[00025] Figure 2 schematically illustrates another example embodiment of a hydrogen concentration sensor.

[00026] Figure 3 schematically illustrates selected portions of a fuel cell power plant including a hydrogen concentration sensor designed according an embodiment of this invention.

DETAILED DESCRIPTION

[00027] Hydrogen concentration sensors designed according to an embodiment of this invention are useful for a variety of purposes. Determining hydrogen concentration for a fuel cell power plant is one example implementation that is discussed below. One feature of embodiments of this invention is that a hydrogen evolving electrode that is distinct from a reference electrode evolves pure hydrogen into a hydrogen chamber where the reference electrode is exposed to the pure hydrogen. This avoids applying any current to the reference electrode and facilitates maintaining a consistent reference potential at the reference electrode, which results in improved sensor performance compared to previous sensors.

[00028] Figure 1 shows an example hydrogen concentration sensor 20. A hydrogen evolving electrode 22 is part of a first electrochemical cell 24 that also includes a hydrogen oxidizing electrode 26 and a matrix 28. In this example, the matrix 28 contains a liquid electrolyte, such as phosphoric acid. The hydrogen evolving electrode 22 introduces pure hydrogen into a hydrogen chamber 30 when a voltage is applied across the hydrogen oxidizing electrode 26 and the hydrogen evolving electrode 22. In the illustrated example the applied voltage is approximately 0.3 volts.

[00029] A reference electrode 32 is situated to be exposed to the pure hydrogen in the hydrogen chamber 30. The reference electrode 32 is part of a second electrochemical cell 34 that also includes a detection electrode 36 and a matrix 38. The matrix 38 in this example also contains a liquid electrolyte, such as phosphoric acid.

[00030] The detection electrode 36 is exposed to gas outside the hydrogen chamber 30 and provides an indication of a concentration of hydrogen in that gas. The illustrated example embodiment utilizes the known Nemst Potential phenomenon as a basis for determining the hydrogen concentration outside of the hydrogen chamber 30. A potential difference (i.e., a voltage) across the detection electrode 36 and the reference electrode 32 provides an indication of the concentration of hydrogen in the gas outside the hydrogen chamber 30.

[00031] In the illustrated example, the hydrogen oxidizing electrode 26 and the detection electrode 36 are exposed to the same gas. At least some hydrogen from that gas is introduced into the hydrogen chamber 30 by the hydrogen evolving electrode 22. The first electrochemical cell 34 reduces protons based on the hydrogen oxidizing electrode 26 being exposed to the gas outside the hydrogen chamber 30. The hydrogen oxidizing electrode 26 has a size and position relative to the detection electrode 36 that does not alter the hydrogen concentration in the gas near the detection electrode 36 to avoid skewing the hydrogen concentration measured by the sensor 20.

[00032] In the illustrated example, the pure hydrogen in the hydrogen chamber 30 is kept from mixing with gas outside the hydrogen chamber 30 by positive pressure within the hydrogen chamber 30. The hydrogen evolving electrode 32 introduces a positive pressure within the hydrogen chamber 30. The size of the hydrogen evolving electrode 32, the amount of pure hydrogen introduced into the hydrogen chamber 30 over time, or both is selectable to provide a desired level of positive pressure within the hydrogen chamber 30.

[00033] The example hydrogen chamber 30 includes a vent 40 that allows pure hydrogen to exit the hydrogen chamber 30. The positive pressure within the hydrogen chamber 30 prevents any gas outside the hydrogen chamber 30 from entering the chamber.

[00034] One feature of the illustrated example is that the reference electrode 32 is distinct from the hydrogen evolving electrode 22. Using the hydrogen evolving electrode 22 to provide the pure hydrogen that keeps the reference electrode 32 at a desired reference potential avoids any need to apply current to the reference electrode. This feature eliminates any shifts in the reference potential that would otherwise occur if the reference electrode 32 were used to evolve pure hydrogen. Having the reference electrode 32 exposed to only pure hydrogen in the hydrogen chamber 30 also ensures a desired potential resulting from the exposure of the reference electrode 32 to the pure hydrogen.

[00035] Another sensor configuration is shown in Figure 2. In this example, the hydrogen evolving electrode 26 and the detection electrode 36 are situated on opposite sides of the sensor 20. This embodiment operates in the same manner as the one shown in Figure 1.

[00036] Hydrogen concentration sensors embodying this invention can be used in a variety of contexts and for various purposes. Figure 3 shows one example implementation in which a sensor 20 is included in a fuel cell power plant 50. A reformer 52 receives a hydrocarbon 54, which may be methane or natural gas for example. The reformer 52 produces a hydrogen fuel at 56 that is supplied to a fuel cell stack assembly 58. The hydrogen fuel is one of the reactants used by the fuel cell stack assembly 58 and oxygen, which may be supplied as air 60, is the other reactant. A hydrogen concentration sensor 20 within the reformer 52 provides information regarding the operation of the reformer 52. A reformer control 62, such as a microprocessor or other computing device, uses the information from the sensor 20 for dynamically adjusting or tuning the operation of the reformer 52. The control 62 does not require any temperature information in this example embodiment, which can provide cost savings compared to systems that require temperature sensors and processing temperature information·

[00037] Hydrogen concentration sensors designed according to an embodiment of this invention are more stable and therefore more reliable than previous sensors that utilize a reference electrode that depends on pure hydrogen to establish the reference potential. Additionally, sensors designed according to an embodiment of this invention can be included in a wider variety of situations where hydrogen level detection is desirable.

[00038] The preceding description is exemplary rather than limiting in nature. Variations and modifications to the disclosed examples may become apparent to those skilled in the art that do not necessarily depart from the essence of this invention. The scope of legal protection given to this invention can only be determined by studying the following claims.