CN104950029A - Oxygen sensor - Google Patents
Oxygen sensor Download PDFInfo
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- CN104950029A CN104950029A CN201410117538.0A CN201410117538A CN104950029A CN 104950029 A CN104950029 A CN 104950029A CN 201410117538 A CN201410117538 A CN 201410117538A CN 104950029 A CN104950029 A CN 104950029A
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- Prior art keywords
- fuel cell
- fuel
- lambda sensor
- cell lambda
- electrolyte
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
- G01N27/26—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating electrochemical variables; by using electrolysis or electrophoresis
- G01N27/403—Cells and electrode assemblies
- G01N27/404—Cells with anode, cathode and cell electrolyte on the same side of a permeable membrane which separates them from the sample fluid, e.g. Clark-type oxygen sensors
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
- G01N27/26—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating electrochemical variables; by using electrolysis or electrophoresis
- G01N27/403—Cells and electrode assemblies
- G01N27/406—Cells and probes with solid electrolytes
- G01N27/407—Cells and probes with solid electrolytes for investigating or analysing gases
- G01N27/409—Oxygen concentration cells
Abstract
The invention provides a fuel cell oxygen sensor. The fuel cell oxygen sensor comprises an oxygen cathode, a diffusion control device, fuel, an electrical catalytic anode and electrolyte, wherein the diffusion control device is used for controlling the speed of diffusing oxygen to the cathode; the electrical catalytic anode can be used for obtaining current by electrochemical oxidization of the fuel; and the fuel is partially or wholly dissolved in the electrolyte.
Description
Technical field
The present invention relates to electrochemical sensor, particularly relate to lambda sensor.
Background technology
From 20th century the seventies, oxygen sensor (galvanic oxygen sensor) is developed and first electrochemical sensor of the marketization.
Its simplest a kind of pattern of lambda sensor based on electrochemical principle work is exactly two electrode systems.Modal pattern comprises lead anode and oxygen cathode.Its working electrode and electrode to be separated by skim electrolytic solution and via a very little resistance UNICOM external circuit.After gas diffuses into sensor, carry out being oxidized or reduction reaction at sensitive electrode surfaces, generation current also flows through two electrodes by external circuit.The size of this electric current and the concentration of gas proportional, the load resistance by external circuit is measured.
In order to enable reaction occur, the current potential of sensitive electrode must remain in a specific scope.But when the concentration of gas increases, kinetic current also increases, so cause changing (polarization) to electrode potential.Because two electrodes are coupled together by a simple load resistance, although the current potential of sensitive electrode also can change along with to the current potential one of electrode.If the concentration of gas constantly raises, the current potential of sensitive electrode finally likely shifts out its allowed band.So far sensor is by non-linear, and the upper concentration that therefore two-electrode gas sensor detects is subject to a definite limitation.
Three-electrode system (i.e. the 3rd electrode, reference electrode and utilize the constant potential operating circuit of an outside) can be introduced to the restriction suffered by polarization of electrode to be avoided.In so a kind of device, sensitive electrode curve keeps a fixed value relative to reference electrode.In reference electrode, no current flows through, and therefore these two electrodes all maintain a constant current potential.Then still can polarize to electrode, but any restriction is not produced to sensor.
Such lambda sensor has lot of advantages.They are compact, reliably, not electricity consumption and can across temperature range operation can be accepted without the need to heating.Although they can provide gratifying performance, its leaded fact is causing concern now, and nowadays people are actively finding new lead-free recipe.The selection of available metal is limited to content and their alloy of periodic table, and the success or not of this classpath is judged by the success substituting plumbous oxygen sensor.
What the unleaded lambda sensor come into the market adopted is above-described three-electrode system, therefore structurally more complicated, and and there is the incompatible problem of pin between the lambda sensor of existing type.
Therefore, people need to develop the unleaded lambda sensor of a kind of employing two electrode systems, its not only compact, reliably, not electricity consumption, can across temperature range operation can be accepted without the need to heating, and environmentally friendly.
Summary of the invention
In view of the above-mentioned subject matter mentioned, the fuel cell lambda sensor of setting forth in the present invention, comprise: oxygen cathode, for controlling the diffusion control device of the speed that oxygen spreads to negative electrode, fuel, the electro-catalysis anode of electric current can be obtained, and electrolyte, described fuel meat or be dissolved in fully in described electrolyte by the electrochemical oxidation of fuel.
In an embodiment of fuel cell lambda sensor of the present invention, negative electrode platiniferous.
In an embodiment of fuel cell lambda sensor of the present invention, negative electrode is containing gold.
In an embodiment of fuel cell lambda sensor of the present invention, negative electrode argentiferous.
In an embodiment of fuel cell lambda sensor of the present invention, negative electrode carbon containing.
In an embodiment of fuel cell lambda sensor of the present invention, diffusion control device is hole.
In an embodiment of fuel cell lambda sensor of the present invention, diffusion control device is microporous barrier.
In an embodiment of fuel cell lambda sensor of the present invention, diffusion control device is non-porous film.
In an embodiment of fuel cell lambda sensor of the present invention, anode platiniferous.
In an embodiment of fuel cell lambda sensor of the present invention, fuel is alcohol.
In an embodiment of fuel cell lambda sensor of the present invention, electrolyte is acid.
In an embodiment of fuel cell lambda sensor of the present invention, electrolyte is alkaline.
In an embodiment of fuel cell lambda sensor of the present invention, the electric current produced is discharged by resistor.
In an embodiment of fuel cell lambda sensor of the present invention, fuel is 1,2-ethylene glycol (ethylene glycol).
In an embodiment of fuel cell lambda sensor of the present invention, fuel is Glycerin (glycerine).
In an embodiment of fuel cell lambda sensor of the present invention, electrolyte sulfur acid.
In an embodiment of fuel cell lambda sensor of the present invention, electrolyte is containing potassium hydroxide.
Accompanying drawing explanation
Fig. 1 is the schematic diagram of fuel cell lambda sensor according to an embodiment of the invention.
Embodiment
In order to understand the present invention better, below in conjunction with accompanying drawing, embodiments of the invention are elaborated.But protection scope of the present invention is not only confined to the following examples.Those skilled in the art can make various changes or modifications the present invention, and these equivalent form of values are equally within the scope of appended claims restriction.
In lambda sensor of the present invention, the oxygen entering sensor from air is tightly controlled by following three kinds of modes usually:
1. little pore;
2. the microporous barrier of low-permeability;
3. non-porous film.
First two mode provide to be directly proportional to oxygen number percent and in effective range value linearly, therefore not by the impact of change of atmospheric pressure.These modes are comparatively conventional, are widely used in industry and pharmacy industry.The third mode provides partial pressure value, and can be used to the specialized application of such as underwater respiring system, usually linear in 100%.
On the other hand, inventor attempts to use other materials to substitute lead electrode with the new unleaded lambda sensor obtained, these equivalent material can comprise some metals in periodic table and alloy thereof, but in fact metal is not the material that uniquely can be used as anode, the material of molecule-fuel that can be oxidized-also can be used as anode.In principle, fuel can be the form of gas, solid or liquid.Gas volume is excessive, is not easy to store, and therefore can not adopt in practical operation.
We consider to use the fuel of solid in the electrolyte dissolving in selected acidity or alkalescence and liquid form.Alkaline electrolyte may be preferred, because non-noble metallic materials can be used for current-carrying, but they are easy to by carbonating, selects alkaline electrolyte to be conducive to the generation suppressing this kind of phenomenon, this factor must be taken into account when selection material.Described carbonating is because the oxidation product of carbon-containing fuel causes, instead of caused by the carbon dioxide in air.Specifically, because the ratio of Carbon Dioxide in Air is originally just very low, even with to introduce the oxygen content of this lambda sensor from air in the mode strictly limited compared with, the content of carbon dioxide also will low several orders of magnitude, and the carbon dioxide therefore in air is not the reason causing non-noble metallic materials carbonating.
The desired characteristic of selected fuel comprises:
1. hypotoxicity, because substitute another kind of toxic ingredient with a kind of toxic ingredient to there is no benefit;
2. low volatility, otherwise fuel can because evaporate and loss;
3. dissolubility in the electrolyte, otherwise fuel cannot react with gratifying degree at anode place;
4. low-freezing, makes fuel/electrolyte mixture to be used for operating in scope wide as far as possible thus;
5. high-energy-density, namely not only has low molecular weight, and each molecule discharges multiple electronics when being oxidized;
6. the oxidation product at anode place should not be preferably insoluble, and must not cause poison electrode catalysts.
Meet most a fluid-like state fuel seemingly liquid polyol that these require, specifically ethylene glycol (1,2-ethylene glycol).Ethylene glycol toxicity is low, and in preferred design, its liquid temperature scope is about-50 ° of C to 100 ° of more than C, and has not observed solid reaction products when exploitation and prototype test.
Therefore, the component part of fuel cell comprises: negative electrode (oxygen electrode), usually containing platinum, gold or silver-colored; Control the diffusion control device of the speed that oxygen spreads to negative electrode; Electro-catalysis anode, preferably comprises platinum black catalyst; And electrolyte/fuel mixture.This fuel cell continued operation, the electric current produced is by being generally the resistors in parallel electric discharge of 100 Ω with the current potential producing 1 to 15 millivolt, and this depends on the diameter of hole or the character of other diffusion controlling mechanisms aforementioned.The electric current producing such current potential is usual in the scope of 10 to 150 milliamperes thus.
Fig. 1 is the schematic diagram of fuel cell lambda sensor according to an embodiment of the invention.
Control by the hole in disk 3 process that oxygen enters sensor from air, this hole is protected by porous PTFE film 1 and 4.At negative electrode 6 place, oxygen molecule is reduced into hydroxide ion.This reaction needed passes through external circuit (normally pull-up resistor) in osculatory 5 supplies electrons from osculatory 8, this electronics is that the fuel by dissolving such as ethylene glycol (1,2-ethylene glycol) is in the electrolyte supplied in the oxidation at catalytic activity anode 7 place.Fuel/electrolyte mixture is kept in container 9, thus the fuel that antianode 7 place consumes supplements.Hydroxide ion shifts to anode to complete internal circuit by electrolyte from negative electrode, makes the imbalance of electric charge be balanced thus.Whole assembly is accommodated in shell 9.The amount of the electric current produced depends on the number percent of oxygen in the air adjacent with sensor inlet.
In an embodiment of the practical operation of the fuel cell lambda sensor shown in Fig. 1, the oxygen in air, through PTFE film 1, in a controlled manner by the hole in disk 3, by PTFE film 4, arrives negative electrode 6.Oxidation reaction is there is in fuel at catalytic activity anode 7 place, the electronics discharged is derived by osculatory 8, arrive osculatory 5 by external circuit (comprising pull-up resistor), then these electronics contact from the oxygen in air with above-mentioned on negative electrode 6, and reduction forms hydroxide ion.The hydroxide ion of this formation moves to anode 7 from negative electrode 6 under electromotive force effect.Described electronics, moving to the process of osculatory 5 by external circuit from osculatory 8, produces corresponding electric current and electromotive force in external circuit, by measuring this electric current and electromotive force, can determine to enter the number percent of oxygen in the air of this sensor exactly.
Two examples of fuel cell lambda sensor of the present invention are below described.
Example 1
Alkaline fuel cell lambda sensor, by au cathode, platinum black anode, the diffusion hole being of a size of 10 to 100 microns and the electrolyte be made up of the ethylene glycol of percentage by weight 25% and the 4M potassium hydroxide of percentage by weight 75%.
Example 2
Acidic fuel cell lambda sensor, by platinum cathode, platinum black anode, the diffusion hole being of a size of 10 to 100 microns and the electrolyte be made up of the ethylene glycol of percentage by weight 75% and the 4M sulfuric acid of percentage by weight 25%.
It will be understood by those skilled in the art that above example is only two examples of fuel cell lambda sensor of the present invention.
Herein described employing two electrode system unleaded lambda sensor not only compact, reliably, not electricity consumption and can across temperature range operation can be accepted without the need to heating, and environmentally friendly.
Claims (17)
1. a fuel cell lambda sensor, comprising:
Oxygen cathode,
For controlling the diffusion control device of the speed that oxygen spreads to negative electrode,
Fuel,
The electro-catalysis anode of electric current can be obtained by the electrochemical oxidation of described fuel, and
Electrolyte, described fuel meat or be dissolved in fully in described electrolyte.
2. fuel cell lambda sensor as claimed in claim 1, is characterized in that, described negative electrode platiniferous.
3. fuel cell lambda sensor as claimed in claim 1, is characterized in that, described negative electrode is containing gold.
4. fuel cell lambda sensor as claimed in claim 1, is characterized in that, described negative electrode argentiferous.
5. fuel cell lambda sensor as claimed in claim 1, is characterized in that, described negative electrode carbon containing.
6. fuel cell lambda sensor as claimed in claim 1, it is characterized in that, described diffusion control device is hole.
7. fuel cell lambda sensor as claimed in claim 1, it is characterized in that, described diffusion control device is microporous barrier.
8. fuel cell lambda sensor as claimed in claim 1, it is characterized in that, described diffusion control device is non-porous film.
9. fuel cell lambda sensor as claimed in claim 1, is characterized in that, described anode platiniferous.
10. fuel cell lambda sensor as claimed in claim 1, it is characterized in that, described fuel is alcohol.
11. fuel cell lambda sensors as claimed in claim 1, it is characterized in that, described electrolyte is acid.
12. fuel cell lambda sensors as claimed in claim 1, it is characterized in that, described electrolyte is alkaline.
13. fuel cell lambda sensors as claimed in claim 1, it is characterized in that, the electric current produced is discharged by resistor.
14. fuel cell lambda sensors as claimed in claim 10, is characterized in that, described fuel is 1,2-ethylene glycol (ethylene glycol).
15. fuel cell lambda sensors as claimed in claim 10, is characterized in that, described fuel is Glycerin (glycerine).
16. fuel cell lambda sensors as claimed in claim 11, is characterized in that, described electrolyte sulfur acid.
17. fuel cell lambda sensors as claimed in claim 12, is characterized in that, described electrolyte is containing potassium hydroxide.
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410117538.0A CN104950029B (en) | 2014-03-26 | 2014-03-26 | Lambda sensor |
| PCT/CN2015/072094 WO2015143954A1 (en) | 2014-03-26 | 2015-02-02 | Oxygen sensor |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410117538.0A CN104950029B (en) | 2014-03-26 | 2014-03-26 | Lambda sensor |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN104950029A true CN104950029A (en) | 2015-09-30 |
| CN104950029B CN104950029B (en) | 2018-10-23 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201410117538.0A Active CN104950029B (en) | 2014-03-26 | 2014-03-26 | Lambda sensor |
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| CN (1) | CN104950029B (en) |
| WO (1) | WO2015143954A1 (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106383155A (en) * | 2016-12-01 | 2017-02-08 | 深圳市深安旭传感技术有限公司 | New-energy vehicle hydrogen sensor with gas diffusion channel |
| CN108254420A (en) * | 2016-12-28 | 2018-07-06 | 深圳市普晟传感技术有限公司 | A kind of hydrogen gas sensor for quickly detection low-concentration hydrogen |
| CN114002298A (en) * | 2021-11-26 | 2022-02-01 | 南京伊桥科技有限公司 | Quick-response catalytic electrode of acid electrolyte oxygen sensor and preparation method |
Citations (7)
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|---|---|---|---|---|
| US5573648A (en) * | 1995-01-31 | 1996-11-12 | Atwood Systems And Controls | Gas sensor based on protonic conductive membranes |
| EP0766085A2 (en) * | 1995-09-28 | 1997-04-02 | Matsushita Electric Industrial Co., Ltd. | Electrochemical device |
| US6080294A (en) * | 1998-07-15 | 2000-06-27 | Atwood Industries, Inc. | Gas sensor with dual electrolytes |
| CN1867825A (en) * | 2003-08-12 | 2006-11-22 | Rae系统股份有限公司 | Solid polymer electrolyte oxygen sensor |
| CN100444435C (en) * | 2004-10-19 | 2008-12-17 | 松下电器产业株式会社 | Membrane electrode assembly, method for producing same and polymer electrolyte fuel cell |
| CN102183566A (en) * | 2011-01-05 | 2011-09-14 | 高国强 | Oxygen volume percent concentration sensor based on capillary chemical corrosion method |
| CN203929706U (en) * | 2014-03-26 | 2014-11-05 | 达特传感器（深圳）有限公司 | Lambda sensor |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2006153568A (en) * | 2004-11-26 | 2006-06-15 | Nissan Motor Co Ltd | Gas measuring instrument |
-
2014
- 2014-03-26 CN CN201410117538.0A patent/CN104950029B/en active Active
-
2015
- 2015-02-02 WO PCT/CN2015/072094 patent/WO2015143954A1/en active Application Filing
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5573648A (en) * | 1995-01-31 | 1996-11-12 | Atwood Systems And Controls | Gas sensor based on protonic conductive membranes |
| EP0766085A2 (en) * | 1995-09-28 | 1997-04-02 | Matsushita Electric Industrial Co., Ltd. | Electrochemical device |
| US6080294A (en) * | 1998-07-15 | 2000-06-27 | Atwood Industries, Inc. | Gas sensor with dual electrolytes |
| CN1867825A (en) * | 2003-08-12 | 2006-11-22 | Rae系统股份有限公司 | Solid polymer electrolyte oxygen sensor |
| CN100444435C (en) * | 2004-10-19 | 2008-12-17 | 松下电器产业株式会社 | Membrane electrode assembly, method for producing same and polymer electrolyte fuel cell |
| CN102183566A (en) * | 2011-01-05 | 2011-09-14 | 高国强 | Oxygen volume percent concentration sensor based on capillary chemical corrosion method |
| CN203929706U (en) * | 2014-03-26 | 2014-11-05 | 达特传感器（深圳）有限公司 | Lambda sensor |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106383155A (en) * | 2016-12-01 | 2017-02-08 | 深圳市深安旭传感技术有限公司 | New-energy vehicle hydrogen sensor with gas diffusion channel |
| CN108254420A (en) * | 2016-12-28 | 2018-07-06 | 深圳市普晟传感技术有限公司 | A kind of hydrogen gas sensor for quickly detection low-concentration hydrogen |
| CN108254420B (en) * | 2016-12-28 | 2024-03-12 | 深圳市普晟传感技术有限公司 | Hydrogen sensor for rapidly detecting low-concentration hydrogen |
| CN114002298A (en) * | 2021-11-26 | 2022-02-01 | 南京伊桥科技有限公司 | Quick-response catalytic electrode of acid electrolyte oxygen sensor and preparation method |
Also Published As
| Publication number | Publication date |
|---|---|
| CN104950029B (en) | 2018-10-23 |
| WO2015143954A1 (en) | 2015-10-01 |
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