CN110749637A - CO electrochemical gas sensor based on semi-solid electrolyte and preparation method thereof - Google Patents
CO electrochemical gas sensor based on semi-solid electrolyte and preparation method thereof Download PDFInfo
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- CN110749637A CN110749637A CN201910899737.4A CN201910899737A CN110749637A CN 110749637 A CN110749637 A CN 110749637A CN 201910899737 A CN201910899737 A CN 201910899737A CN 110749637 A CN110749637 A CN 110749637A
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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
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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
- G01N27/4073—Composition or fabrication of the solid electrolyte
- G01N27/4074—Composition or fabrication of the solid electrolyte for detection of gases other than oxygen
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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
- G01N27/4075—Composition or fabrication of the electrodes and coatings thereon, e.g. catalysts
Abstract
The invention provides a CO electrochemical gas sensor based on semi-solid electrolyte, which comprises: a working electrode, a diaphragm, a solid high polymer electrolyte, a counter electrode, a reference electrode, a hydrophilic porous material for adsorbing an acid electrolyte and a pin outside the shell are sequentially arranged in the sensor shell; the sensor shell is provided with a top cover, and the sensor further comprises an activated carbon material positioned on the inner side of the top cover. The CO electrochemical gas sensor based on the semi-solid electrolyte and the preparation method thereof can prolong the service life of the sensor.
Description
Technical Field
The invention belongs to the technical field of CO gas sensors, and particularly relates to a CO electrochemical gas sensor based on semi-solid electrolyte and a preparation method thereof.
Background
CO is a colorless and tasteless toxic gas and is a flammable and explosive gas, and can form an explosive mixture when being mixed with air, and the explosive mixture can cause combustion and explosion when meeting open fire and high temperature, so that the safety of industrial and mining personnel is seriously harmed, and therefore, how to efficiently and quickly detect the CO gas becomes an important subject.
The electrochemical CO gas sensor has the advantages of high sensitivity, good repeatability, high response speed, long service life and the like, and is widely applied to disaster prevention and alarm of factories, mines, families and the like. The CO detection plays an important role in daily production and life. Therefore, research on electrochemical CO sensors is of great interest. The sensitivity and response time of the electrochemical CO sensor mainly depend on a working electrode and a counter electrode, the improvement of the activity of the noble metal catalyst is a technical key, the service life of the sensor is determined by an electrolyte, and the research of selecting a proper electrolyte to prolong the service life of the sensor is carried out by researchers at present. At present, a traditional electrochemical CO sensor is mainly based on a liquid electrolyte type sensor, but the liquid electrochemical CO gas sensor has the defects that electrolyte is volatile and easy to leak and a circuit is corroded, and in addition, although the CO sensor based on all-solid electrolyte does not have the problem of electrolyte leakage, the CO sensor is easy to be influenced by an external environment, particularly humidity. In the prior art, the two types of sensors cause deviation of measurement data.
Therefore, it is necessary to provide a new electrolyte CO gas sensor to solve the above problems.
Disclosure of Invention
In view of the drawbacks of the prior art, it is an object of the present invention to provide a CO gas sensor based on a semi-solid electrolyte.
In order to achieve the above purposes, the invention adopts the technical scheme that: a CO electrochemical gas sensor based on a semi-solid electrolyte, the sensor comprising: a working electrode, a diaphragm, a solid high polymer electrolyte, a counter electrode, a reference electrode, a hydrophilic porous material for adsorbing an acid electrolyte and a pin outside the shell are sequentially arranged in the sensor shell;
the sensor shell is provided with a top cover, and the sensor further comprises an activated carbon material positioned on the inner side of the top cover.
Further, be equipped with the gas pocket on the top cap, the sensor still includes the waterproof ventilated membrane that is located the adhesion top cap outside.
Further, the working electrode, the counter electrode or the reference electrode comprise 20-60% of noble metal and carbon material, and the noble metal is at least one of platinum, ruthenium, iridium, gold and silver.
Further, the hydrophilic porous material is a cellulose membrane.
Further, the diaphragm is a polystyrene sulfonic acid film.
Further, the solid polymer electrolyte is a perfluorinated sulfonic acid copolymer membrane.
Further, the acid electrolyte is mainly H2SO4The concentration is 3 to 9 mol/L.
Further, the sensor shell is made of one or more of PC, ABS and PP materials.
The invention also provides a preparation method of the CO electrochemical gas sensor based on the semi-solid electrolyte, which comprises the following steps:
1) using carbon paper or PTFE as a substrate, loading 20-60% of at least one of Pt/Ru/Au/Ag on the hydrophilic surface of the carbon paper or PTFE by using an ultrasonic spraying or screen printing mode, and compounding the Pt/Ru/Au/Ag and the carbon material to obtain a catalytic material, and cutting the prepared working electrode, counter electrode and reference electrode according to the fixed size of the sensor;
2) pretreating solid polymer electrolyte with 5% H at 80 deg.C2O2Decocting in solution for 1H, at 80 deg.C H2SO4Boiling the solution for 1h, boiling the solution in deionized water for 1h, and then putting the solution in the deionized water for later use;
3) a working electrode, a diaphragm, a solid high polymer electrolyte, a counter electrode, a reference electrode and a hydrophilic porous material for adsorbing an acid electrolyte are sequentially arranged in a sensor shell, and the working electrode, the counter electrode and the reference electrode are connected with leads at pins to form a flow path;
4) and fixing the dustproof film on the outer side of the top cover, placing the activated carbon material on the inner side of the top cover, and packaging the top cover and the shell by utilizing ultrasonic welding.
The invention has the advantages that a small part of the adsorbed H is stored at the bottom of the sensor shell by mixing the perfluorinated sulfonic acid copolymer membrane with the liquid absorbing material2SO4The liquid absorption material, placed perfluorosulfonic acid copolymer membrane simultaneously on contact counter electrode and reference electrode surface, form relay effect, form an ion transfer effect with the liquid absorption material cooperation of bottom to can accelerate the speed of reaction, on the other hand, along with the extension of reaction time, electrolyte loss back, solid polymer electrolyte perfluorosulfonic acid copolymer membrane can self release the ion, maintains that whole reaction continues to go on, the life-span of extension sensor.
Drawings
FIG. 1 is a schematic diagram of a structure of a CO gas sensor based on a semi-solid electrolyte;
fig. 2 is a graph of response time performance of a CO gas sensor based on a semi-solid electrolyte.
In the figure: 1-waterproof breathable film; 2-a top cover; 3-an activated carbon material; 4-a working electrode; 5-a separator; 6-solid high polymer electrolyte; 7-a counter electrode; 8-a reference electrode; 9-hydrophilic porous material; 10-pin.
Detailed Description
In order to make the technical problems solved, the technical solutions adopted, and the technical effects achieved by the present invention clearer, the technical solutions of the embodiments of the present invention will be further described in detail with reference to the accompanying drawings. It is to be understood that the described embodiments are merely exemplary of the invention, and not restrictive of the full scope of the invention. All other embodiments, which can be obtained by a person skilled in the art without any inventive step based on the embodiments of the present invention, are within the scope of the present invention.
Referring to fig. 1, fig. 1 is a schematic structural view of a CO gas sensor based on a semi-solid electrolyte. The invention provides a CO electrochemical gas sensor based on semi-solid electrolyte, which comprises: the sensor comprises a working electrode 4, a diaphragm 5, a solid high polymer electrolyte 6, a counter electrode 7, a reference electrode 8, a hydrophilic porous material 9 for adsorbing acid electrolyte and a pin 10 outside the shell, wherein the working electrode 4, the reference electrode 8 and the counter electrode 7 are sequentially arranged in the shell of the sensor, and leads at the pin 10 are arranged on the working electrode 4, the reference electrode 8 and the counter electrode 7 to form a loop.
The sensor shell is provided with a top cover 2, and the sensor further comprises an activated carbon material 3 positioned on the inner side of the top cover 2.
The top cover 2 is provided with an air hole, and the sensor further comprises a waterproof breathable film 1 positioned outside the adhesion top cover 2.
The working electrode 4 is a noble metal and is compounded with some carbon materials. Specifically, the alloy comprises 20-60% of noble metal and carbon material, wherein the noble metal is at least one of platinum, ruthenium, iridium, gold and silver.
The counter electrode 7 is a noble metal and is compounded with some carbon material. Specifically, the alloy comprises 20-60% of noble metal and carbon material, wherein the noble metal is at least one of platinum, ruthenium, iridium, gold and silver.
The reference electrode 8 is a noble metal and is compounded with some carbon materials. Specifically, the alloy comprises 20-60% of noble metal and carbon material, wherein the noble metal is at least one of platinum, ruthenium, iridium, gold and silver.
The hydrophilic porous material 9 is a cellulose membrane.
The diaphragm 5 is a polystyrene sulfonic acid film.
The solid polymer electrolyte 6 is a perfluorosulfonic acid copolymer membrane.
The acidic electrolyte is mainly H2SO4The concentration is 3 to 9 mol/L.
The sensor shell is made of one or more of PC, ABS and PP materials.
The invention also provides a preparation method of the CO electrochemical gas sensor based on the semi-solid electrolyte, which comprises the following steps:
1) by utilizing an ultrasonic spraying or screen printing mode, taking carbon paper or PTFE (polytetrafluoroethylene) as a substrate, loading at least one of 20-60% of Pt/Ru/Au/Ag on the hydrophilic surface of the substrate and compounding the Pt/Ru/Au/Ag with a carbon material, and cutting the prepared working electrode, counter electrode and reference electrode according to the fixed size of the sensor;
2) pretreating solid polymer electrolyte with 5% H at 80 deg.C2O2Decocting in solution for 1 hr to remove corresponding organic impurities, and removing H at 80 deg.C2SO4Boiling the solution for 1h to protonate the perfluorinated sulfonic acid copolymer membrane, boiling the solution in deionized water for 1h, and then putting the solution into the deionized water for later use;
3) a working electrode, a diaphragm, a solid high polymer electrolyte, a counter electrode, a reference electrode and a hydrophilic porous material for adsorbing an acid electrolyte are sequentially arranged in a sensor shell, and the working electrode, the counter electrode and the reference electrode are connected with leads at pins to form a flow path;
wherein, the solid polymer electrolyte provides ions required by the reaction, a small part of H is stored at the bottom of the sensor shell and is adsorbed by the H through the mixed use of the perfluorinated sulfonic acid copolymer membrane and the liquid absorption material2SO4The liquid absorption material, placed perfluorosulfonic acid copolymer membrane on counter electrode and reference electrode surface simultaneously, form relay effect, form an ion transfer effect with the liquid absorption material cooperation of bottom to can accelerate the speed of reaction, on the other hand, along with the extension of reaction time, behind the electrolyte loss, solid polymer electrolyte perfluorosulfonic acid copolymer membrane can self release the ion, keeps whole reaction to go on, prolongs the life-span of sensor.
4) And fixing the dustproof film on the outer side of the top cover, placing the activated carbon material on the inner side of the top cover, and packaging the top cover and the shell by utilizing ultrasonic welding.
The performance of the CO sensor of the present invention was tested, and in one specific embodiment, 400ppm CO gas was selected for performance testing, the aeration flow was 0.8L/min, and timing was started after aeration, with the test results shown in fig. 2. As can be seen from the figure, the response time of the sensor to CO is about 20s, and the response speed is high. Meanwhile, stability test is carried out from the completion of assembly, and the sensor has stable performance after half a year of test, and the performance of the sensor is only attenuated by 2% in 6 months, which shows that the sensor has better service life.
Compared with the prior art, the CO electrochemical gas sensor based on the semi-solid electrolyte and the preparation method thereof provided by the invention have the advantages that the solid polymer electrolyte and the hydrophilic porous material for adsorbing the acidic electrolyte are mixed for use, so that the response speed of the CO electrochemical gas sensor can be better increased, and the service life of the sensor can be prolonged. The solid polymer electrolyte solves the main problems existing in the liquid electrolyte at present, such as the defects of easy drying, easy leakage, difficult sealing and the like, but the solid polymer electrolyte is easily influenced by the temperature and the humidity of the environment, a certain amount of acid electrolyte is stored to stabilize the solid polymer electrolyte by utilizing a hydrophilic porous material for adsorbing the acid electrolyte, and meanwhile, in the environment of the hydrophilic porous material for adsorbing the electrolyte, the ion transfer capacity of the solid polymer electrolyte is enhanced on one hand, and on the other hand, the solid polymer electrolyte can spontaneously supplement the electrolyte in the use process of the sensor, so that the quick response of the sensor to CO and the longer service life are better realized.
It will be understood by those skilled in the art that the CO electrochemical gas sensor based on a semi-solid electrolyte and the method for manufacturing the same according to the present invention are not limited to the examples described in the detailed description, and the above detailed description is only for the purpose of explaining the present invention and is not intended to limit the present invention. Other embodiments will be apparent to those skilled in the art from the following detailed description, which is intended to cover all modifications, equivalents, and alternatives falling within the spirit and scope of the invention as defined by the appended claims.
Claims (9)
1. A CO electrochemical gas sensor based on a semi-solid electrolyte, the sensor comprising:
a working electrode, a diaphragm, a solid high polymer electrolyte, a counter electrode, a reference electrode, a hydrophilic porous material for adsorbing an acid electrolyte and a pin outside the shell are sequentially arranged in the sensor shell;
the sensor shell is provided with a top cover, and the sensor further comprises an activated carbon material positioned on the inner side of the top cover.
2. A semi-solid electrolyte based CO electrochemical gas sensor according to claim 1, wherein the top cover is provided with an air hole, the sensor further comprising a water-proof gas permeable membrane located outside the adhesive top cover.
3. A semi-solid electrolyte based CO electrochemical gas sensor according to claim 1, wherein the working, counter or reference electrode comprises 20% to 60% of a noble metal and a carbon material, the noble metal being at least one of platinum, ruthenium, iridium, gold and silver.
4. The semi-solid electrolyte based CO electrochemical gas sensor according to claim 1, wherein the hydrophilic porous material is a cellulose membrane.
5. The semi-solid electrolyte based CO electrochemical gas sensor of claim 1, wherein the separator is a polystyrene sulfonic acid membrane.
6. The semi-solid electrolyte based CO electrochemical gas sensor according to claim 1, wherein the solid high polymer electrolyte is a perfluorosulfonic acid copolymer membrane.
7. The semi-solid electrolyte based CO electrochemical gas sensor of claim 1, wherein the acidic electrolyte is primarily H2SO4The concentration is 3 to 9 mol/L.
8. The semi-solid electrolyte based CO electrochemical gas sensor of claim 1, wherein the sensor housing is one or more of PC, ABS, PP material.
9. A method of manufacturing a semi-solid electrolyte based CO electrochemical gas sensor according to any one of claims 1-8, characterized in that the method of manufacturing comprises the steps of:
1) using carbon paper or PTFE as a substrate, loading 20-60% of at least one of Pt/Ru/Au/Ag on the hydrophilic surface of the carbon paper or PTFE by using an ultrasonic spraying or screen printing mode, and compounding the carbon paper with the carbon material, and cutting the prepared working electrode, counter electrode and reference electrode according to the fixed size of the sensor;
2) pretreating solid polymer electrolyte with 5% H at 80 deg.C2O2Decocting in solution for 1H, at 80 deg.C H2SO4Boiling the solution for 1h, boiling the solution in deionized water for 1h, and then putting the solution in the deionized water for later use;
3) a working electrode, a diaphragm, a solid high polymer electrolyte, a counter electrode, a reference electrode and a hydrophilic porous material for adsorbing an acid electrolyte are sequentially arranged in a sensor shell, and the working electrode, the counter electrode and the reference electrode are connected with leads at pins to form a flow path;
4) and fixing the dustproof film on the outer side of the top cover, placing the activated carbon material on the inner side of the top cover, and packaging the top cover and the shell by utilizing ultrasonic welding.
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| CN201910899737.4A CN110749637A (en) | 2019-09-23 | 2019-09-23 | CO electrochemical gas sensor based on semi-solid electrolyte and preparation method thereof |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114441619A (en) * | 2022-01-28 | 2022-05-06 | 安徽大学 | Electrode substrate of solid electrochemical gas sensor and sensor manufacturing method |
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| US20060196770A1 (en) * | 2005-03-04 | 2006-09-07 | Figaro Engineering Inc. | Liquid electrochemical gas sensor |
| CA2508384A1 (en) * | 2005-05-26 | 2006-11-26 | City Technology Limited | Electrochemical gas sensor |
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