CN111413386A - Based on YSZ and MTiO3Mixed potential type acetylene sensor of sensitive electrode and preparation method thereof - Google Patents
Based on YSZ and MTiO3Mixed potential type acetylene sensor of sensitive electrode and preparation method thereof Download PDFInfo
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- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 title claims abstract description 46
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 title claims abstract description 46
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- 239000000758 substrate Substances 0.000 claims abstract description 28
- 238000010438 heat treatment Methods 0.000 claims abstract description 20
- 229910052793 cadmium Inorganic materials 0.000 claims abstract description 15
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 15
- 239000000919 ceramic Substances 0.000 claims abstract description 14
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 45
- 239000007772 electrode material Substances 0.000 claims description 30
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 15
- 238000004519 manufacturing process Methods 0.000 claims description 14
- 238000000034 method Methods 0.000 claims description 14
- 239000002002 slurry Substances 0.000 claims description 12
- 238000005245 sintering Methods 0.000 claims description 11
- 238000003756 stirring Methods 0.000 claims description 11
- 238000002156 mixing Methods 0.000 claims description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- 239000000853 adhesive Substances 0.000 claims description 6
- 230000001070 adhesive effect Effects 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 5
- 229910052593 corundum Inorganic materials 0.000 claims description 5
- 239000000843 powder Substances 0.000 claims description 5
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims description 5
- 229910001845 yogo sapphire Inorganic materials 0.000 claims description 5
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 claims description 4
- 238000001816 cooling Methods 0.000 claims description 4
- 235000019353 potassium silicate Nutrition 0.000 claims description 4
- 238000003466 welding Methods 0.000 claims description 4
- WUOACPNHFRMFPN-UHFFFAOYSA-N alpha-terpineol Chemical compound CC1=CCC(C(C)(C)O)CC1 WUOACPNHFRMFPN-UHFFFAOYSA-N 0.000 claims description 3
- 239000008367 deionised water Substances 0.000 claims description 3
- 229910021641 deionized water Inorganic materials 0.000 claims description 3
- SQIFACVGCPWBQZ-UHFFFAOYSA-N delta-terpineol Natural products CC(C)(O)C1CCC(=C)CC1 SQIFACVGCPWBQZ-UHFFFAOYSA-N 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 3
- 238000004806 packaging method and process Methods 0.000 claims description 3
- 229940116411 terpineol Drugs 0.000 claims description 3
- 229910003243 Na2SiO3·9H2O Inorganic materials 0.000 claims description 2
- 238000001035 drying Methods 0.000 claims description 2
- 239000004115 Sodium Silicate Substances 0.000 claims 1
- 239000000956 alloy Substances 0.000 claims 1
- 229910045601 alloy Inorganic materials 0.000 claims 1
- 229910052911 sodium silicate Inorganic materials 0.000 claims 1
- 230000035945 sensitivity Effects 0.000 abstract description 17
- 238000001514 detection method Methods 0.000 abstract description 11
- 239000000463 material Substances 0.000 abstract description 6
- 239000002131 composite material Substances 0.000 abstract description 4
- 229910001233 yttria-stabilized zirconia Inorganic materials 0.000 description 31
- 239000007789 gas Substances 0.000 description 17
- 229910002979 CdTiO3 Inorganic materials 0.000 description 16
- 238000012360 testing method Methods 0.000 description 8
- 229910019096 CoTiO3 Inorganic materials 0.000 description 6
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 6
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 5
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 3
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 3
- 239000005977 Ethylene Substances 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 3
- 229910002091 carbon monoxide Inorganic materials 0.000 description 3
- 239000007784 solid electrolyte Substances 0.000 description 3
- 229910002076 stabilized zirconia Inorganic materials 0.000 description 3
- 241000627951 Osteobrama cotio Species 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 229910021529 ammonia Inorganic materials 0.000 description 2
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000003980 solgel method Methods 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- 238000004566 IR spectroscopy Methods 0.000 description 1
- 229910020489 SiO3 Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 238000001626 infrared photoacoustic spectroscopy Methods 0.000 description 1
- 238000009421 internal insulation Methods 0.000 description 1
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(II) nitrate Inorganic materials [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 1
- 238000000643 oven drying Methods 0.000 description 1
- 238000001560 photoacoustic Raman spectroscopy Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000007650 screen-printing Methods 0.000 description 1
- DCKVNWZUADLDEH-UHFFFAOYSA-N sec-butyl acetate Chemical compound CCC(C)OC(C)=O DCKVNWZUADLDEH-UHFFFAOYSA-N 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- LLZRNZOLAXHGLL-UHFFFAOYSA-J titanic acid Chemical compound O[Ti](O)(O)O LLZRNZOLAXHGLL-UHFFFAOYSA-J 0.000 description 1
- 229930195735 unsaturated hydrocarbon Natural products 0.000 description 1
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- 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
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Abstract
Based on YSZ and MTiO3A mixed potential type acetylene sensor with a (M is Cd, Ni or Co) sensitive electrode and a preparation method thereof belong to the technical field of gas sensors. The sensor is made of Al with Pt heating electrode2O3Ceramic plate, YSZ substrate, Pt reference electrode and MTiO3A sensitive electrode; the reference electrode and the sensitive electrode are separately and symmetrically arranged at two ends of the upper surface of the YSZ substrate, the lower surface of the YSZ substrate and Al with a Pt heating electrode2O3The ceramic plates are bonded together. The invention uses YSZ as ion conductive layer and MTiO3The (M is Cd, Ni or Co) composite oxide material is used as a sensitive electrode, and the discovery shows that CdTiO is used3The device which is a sensitive electrode shows the highest response, and in addition, the device also shows good sensitivity, lower detection lower limit, good selectivity and stability.
Description
Technical Field
The invention belongs to the technical field of gas sensors, and particularly relates to a gas sensor based on YSZ and MTiO3The mixed potential type acetylene sensor with Cd, Ni or Co sensitive electrode and its preparation process are mainly used in fast detection of volatile acetylene.
Background
Acetylene (C)2H2) Is an important flammable and extremely unstable unsaturated hydrocarbon gas, and has colorless and unique odor. C is generated when the internal insulation of the power transformer equipment is failed2H2Thus, a reliable, real-time, high-sensitivity C was developed2H2The detection device has important significance for timely and effectively avoiding potential risks of the power transformer and judging fault types.
To date, many research teams have used various methods to detect acetylene gas in different applications, such as gas chromatography, infrared spectroscopy, photoacoustic spectroscopy, and raman spectroscopy. However, the conventional process has the characteristics of large volume, high processing precision, high price and the like, so that the application of the conventional process is limited to a certain extent. Aiming at the defects, the development of a gas sensor with high performance and simple structure is of great significance. Among the numerous types of gas sensors, semiconductor gas sensors have been extensively studied over the past few decades. In addition, the yttrium-stabilized zirconia solid electrolyte type sensor has become an important choice due to the advantages of high sensitivity, good stability, simple structure, low cost and the like. However, mixed potential type C based on YSZ2H2The sensor has less research on the design of the sensing electrode material. Therefore, a great deal of work is required to develop YSZ-based C2H2Gas sensor and a method for manufacturing the sameThe sensing performance is improved.
Disclosure of Invention
The invention aims to provide a catalyst based on YSZ and MTiO3The mixed potential type acetylene sensor with the (M being Cd, Ni or Co) sensitive electrode and the preparation method thereof realize the requirement of quickly detecting acetylene, effectively improve the sensitivity of the sensor, reduce the performance of detection lower limit and the like, and promote the practical application of the sensor in the field of acetylene detection. The sensor obtained by the invention has the advantages of high response speed, high sensitivity, lower detection lower limit, and good selectivity and stability.
The ultra-fast response acetylene sensor is based on a stabilized zirconia (YSZ) solid electrolyte and MTiO3(M is Cd, Ni or Co) composite oxide sensitive electrode, YSZ (yttria-stabilized zirconia (8% mol of Y)2O3-ZrO2) As an ion conductive layer.
The invention is based on YSZ and MTiO3(M is Cd, Ni or Co) sensitive electrode, as shown in FIG. 1, from bottom to top by Al with Pt heating electrode2O3The ceramic plate, the YSZ substrate, the strip Pt reference electrode and the strip sensitive electrode; the Pt reference electrode and the sensitive electrode are separately and symmetrically arranged at two ends of the upper surface of the YSZ substrate, the lower surface of the YSZ substrate and the Al with the Pt heating electrode2O3One surface of the Pt heating electrode of the ceramic plate is bonded together; the sensitive electrode material is MTiO3(M is Cd, Ni or Co), and is prepared by the following method:
mixing M (NO)3)2·nH2O dissolution (respectively Cd (NO)3)2·4H2O，Ni(NO3)2·6H2O，Co(NO3)2·6H2O) dissolving in ethanol at room temperature by stirring; adding tetrabutyl titanate into the solution, continuously stirring uniformly, adding citric acid and water, stirring at room temperature to form uniform sol, and standing for 20-30 hours to obtain gel; m (NO)3)2·nH2O, titanic acid tetraThe molar ratio of the butyl ester to the citric acid is 1: 1: 2; drying the obtained gel for 12-24 hours at 80-90 ℃ under a vacuum condition to obtain dry gel, and finally sintering the dry gel for 1-3 hours at 900-1100 ℃ to obtain MTiO3(M is Cd, Ni or Co) sensitive electrode material;
c according to the invention2H2The preparation steps of the sensor are as follows:
(1) manufacturing a Pt reference electrode: manufacturing a strip-shaped Pt reference electrode with the thickness of 15-20 microns at one end of the upper surface of the YSZ substrate by using Pt slurry, folding a Pt wire, adhering the Pt wire to the middle position of the reference electrode to be used as an electrode lead, baking the YSZ substrate at 90-120 ℃ for 1-2 hours, sintering the YSZ substrate at 1000-1100 ℃ for 1-2 hours, removing terpineol in the Pt slurry, and cooling to room temperature;
(2) preparation of MTiO3(M is Cd, Ni or Co) sensitive electrode: mixing MTiO3(M is Cd, Ni or Co) sensitive electrode material is mixed into slurry with deionized water, and the mass concentration is 2-20%; by MTiO3Preparing a strip-shaped sensitive electrode with the thickness of 20-30 microns at the other end of the upper surface of the YSZ substrate, which is symmetrical to the reference electrode, of the slurry (M is Cd, Ni or Co), and folding a platinum wire in half and then adhering the platinum wire to the middle position of the sensitive electrode to be used as an electrode lead;
(3) sintering the YSZ substrate with the reference electrode and the sensitive electrode prepared in the step (2) at 800-1000 ℃ for 1-3 hours; the heating rate during high-temperature sintering is 1-2 ℃/min;
(4) preparing an inorganic adhesive: water glass (Na) is measured2SiO3·9H2O)2 to 4m L, and weighing Al2O30.7-1.0 g powder, mixing water glass and Al2O3Mixing and uniformly stirring the powder to prepare an inorganic adhesive;
(5) using inorganic adhesive to make the lower surface of YSZ substrate and Al with Pt heating electrode2O3One surface of the Pt heating electrode of the ceramic plate is bonded together;
in which Al with Pt heating electrode2O3The ceramic plate is made of Al2O3Obtained by screen-printing Pt on ceramic plates, with Pt plusAl of thermode2O3The ceramic plate is used as a heating plate of the sensor;
(6) welding and packaging the device obtained in the step (5) to obtain the YSZ and MTiO-based device3The mixed potential type acetylene sensor with sensitive electrodes.
The invention uses stable zirconia (YSZ) as an ion conducting layer and MTiO with high electrochemical catalytic activity3(M is Cd, Ni or Co) composite oxide material as sensitive electrode to respectively construct three kinds of sensing devices, and comparing C at high temperature2H2The invention has the advantages that the device with higher sensitivity performance is obtained:
(1) the method utilizes a typical solid electrolyte, namely stabilized zirconia (YSZ), has good thermal stability and chemical stability, and can detect acetylene in a complex environment;
(2) preparation of high-performance composite oxide MTiO by simple sol-gel method3(M is Cd, Ni or Co) as a sensitive electrode of the sensor, and the preparation method is simple and is beneficial to batch industrial production.
(3) The performance of a sensor constructed by comparing three novel perovskite type sensitive electrode materials shows that the CdTiO is3YSZ-based mixed potential device pair C as sensitive electrode2H2Shows the highest response, has lower detection lower limit, good sensitivity, selectivity and stability, and is shown in C2H2The detection aspect has potential application prospect.
Drawings
FIG. 1: the structure schematic diagram of the YSZ-based mixed potential type acetylene sensor is provided.
The names of the parts are as follows: pt filament 1, MTiO3(M is Cd, Ni or Co) sensitive electrode 2, YSZ substrate 3, Pt reference electrode 4, Pt dots (for sticking electrode lead) 5, inorganic adhesive 6, Al with Pt heating electrode2O3A ceramic plate 7.
FIG. 2: XRD patterns (wherein, the abscissa is angle, and the ordinate is intensity) of the three sensitive electrode materials prepared by the invention.
Shown in FIG. 2 as CdTiO3、NiTiO3And CoTiO3The XRD pattern of the sensitive electrode material is compared with a standard spectrogram, and the three synthesized sensitive electrode materials are respectively consistent with JCPDS (File No.78-1015, 76-334 and 1-1040) of a standard card, which shows that the sensitive electrode material prepared by the invention is pure-phase CdTiO3、NiTiO3And CoTiO3A material.
FIG. 3: respectively utilizing CdTiO at the working temperature of 550 DEG C3、NiTiO3And CoTiO3Sensor pair constructed as sensitive electrode material and having 100ppm C2H2Response value versus curve.
The sensitivity test of the device adopts a static test method (the specific process is shown in the embodiment), and the response value of the sensor is delta V-VC2H2-VAir (a)And (4) showing. As shown in FIG. 3, the device pairs made in examples 1, 2 and 3 are 100ppm C2H2The response values of the samples are compared with each other, and it can be seen from the graph that the devices obtained in examples 1, 2 and 3 are 100ppm C2H2The response values of (a) were-126, -4.6 and-4.2 mV, respectively. Thus, CdTiO3YSZ-based mixed potential type C as sensitive electrode material2H2The sensor has the highest response value.
FIG. 4: using CdTiO3Sensor pair C as sensitive electrode material2H2In which the abscissa is C2H2The logarithm of the concentration, the ordinate is the potential difference; the operating temperature is 550 degrees).
The sensitivity of the sensor is the slope of the linear relationship between the response value of the sensor and the corresponding concentration logarithm in a certain measured concentration range. As shown in FIG. 4, for utilizing CdTiO3Sensor pair C as sensitive electrode material2H2The sensitivity curve of (A) shows that the device pairs are 0.5-5 ppm and 5-100 ppm C2H2The sensitivity of (a) is-8 mV/decade and-91 mV/decade, and the lowest can detect 500ppb of C2H2The sensor shows good sensitivity and a lower detection limit.
FIG. 5: using CdTiO3Selective stereograms and selective bar charts of mixed gases at different operating temperatures of the sensor as sensitive electrode material. (wherein, a, the X coordinate is the working temperature, the Y coordinate is the testing gas which is respectively ethylene, methane, carbon monoxide, hydrogen and ammonia from bottom to top, and the Z coordinate is the potential difference value; b, the abscissa is the potential difference value, and the ordinate is the testing gas which is respectively ammonia + acetylene, hydrogen + acetylene, carbon monoxide + acetylene, methane + acetylene and ethylene + acetylene from bottom to top);
shown in FIG. 5 as CdTiO3The selectivity curve of the sensor as sensitive electrode material, as can be seen from the figure, device pair C2H2The device has the greatest sensitivity, and the response of other interference gases is low, so that the device has good selectivity. In the graph b, the response values of ammonia gas + acetylene, hydrogen gas + acetylene, carbon monoxide + acetylene, methane + acetylene and ethylene + acetylene are not changed much compared with the response value of pure acetylene gas, which indicates that the influence of interference gas on the performance of the device is small.
FIG. 6: with CdTiO3Stability curves of the sensor as sensitive electrode material (where the abscissa is time and the ordinate is relative humidity and potential difference, respectively).
The stability of the device is tested by keeping the sensor at 550 ℃ working temperature and testing 100ppm C under the condition of continuous high temperature for 30 days2H2The response value of (c) was used as a standard, and a point was taken every three days during the test to record the change over 30 days. As shown in FIG. 6, is made of CdTiO3The stability of the device as a sensitive electrode material is tested within 30 days, and as can be seen from the figure, the device is matched with 100ppm C within 30 days2H2The fluctuation range of the variation of the response values is less than 25%, which indicates that the device has better stability.
Detailed Description
Example 1:
preparation of CdTiO by sol-gel method3Material, CdTiO sintered at 1000 deg.C3Preparation of YSZ-based mixed potential acetylene as sensitive electrode materialThe sensor and the gas-sensitive performance of the sensor are tested, and the specific process is as follows:
1. manufacturing a Pt reference electrode, namely manufacturing a strip-shaped Pt reference electrode with the size of 0.5mm × 2mm and the thickness of 15 mu m on one end of the upper surface of a YSZ substrate with the length, width and thickness of 2 × 2mm and the thickness of 0.2mm by using Pt slurry, folding a Pt wire, adhering the Pt wire to the middle position of the reference electrode, leading out an electrode lead, baking the YSZ substrate at 100 ℃ for 1.5 hours, sintering the YSZ substrate at 1000 ℃ for 1 hour, removing terpineol in the Pt slurry, and finally cooling to the room temperature.
2. Preparation of CdTiO3A sensitive electrode: weighing 5mmol Cd (NO)3)2·4H2Dissolving O in 15m L ethanol, stirring at room temperature to dissolve, adding 5mmol tetrabutyl titanate into the solution, stirring, adding 10mmol citric acid and 15m L water, stirring at room temperature to form uniform sol, standing for 24 hr, oven drying the obtained gel at 80 deg.C under vacuum for 24 hr to obtain xerogel, and sintering at 1000 deg.C for 3 hr to obtain CdTiO3And (3) sensitive electrode material.
5mg of CdTiO are taken3Mixing the powder with deionized water 100mg to obtain slurry, and mixing with CdTiO3The other end of the upper surface of the YSZ substrate, which is symmetrical to the reference electrode, of the slurry is coated with a strip-shaped sensitive electrode with the size of 0.5mm × 2mm and the thickness of 20 microns, and a platinum wire is also used for being folded in half and then adhered to the sensitive electrode to lead out an electrode lead.
And heating the prepared YSZ substrate with the reference electrode and the sensitive electrode to 800 ℃ at the heating rate of 2 ℃/min, keeping the temperature for 2 hours, and then cooling to room temperature.
3. A ceramic plate having a heating electrode is bonded. Using an inorganic binder (Al)2O3And water glass Na2SiO3·9H2O, mass to volume ratio of 1 g: 4m L) the lower surface (the side not coated with the electrode) of the YSZ substrate was brought into contact with the same size of Al with Pt heater electrode2O3The ceramic plate (length, width, 2 × 2mm, thickness, 0.2mm) Pt heating electrode was bonded on one side.
4. And welding and packaging the device. And welding the device on a hexagonal tube seat, sleeving a protective cover on the hexagonal tube seat, and manufacturing the hybrid potential type acetylene sensor.
Example 2:
NiTiO sintered at 1000 deg.C3The material is used as a sensitive electrode material to manufacture an acetylene sensor, and the manufacturing process comprises the following steps:
NiTiO prepared by the method3Sintering the mixture in a muffle furnace at 1000 ℃ to obtain the NiTiO sensitive electrode material3The device fabrication process was the same as in example 1.
Example 3:
CoTiO sintered at 1000 deg.C3The material is used as a sensitive electrode material to manufacture an acetylene sensor, and the manufacturing process comprises the following steps:
CoTiO prepared by the method3Sintering the mixture in a muffle furnace at 1000 ℃ to obtain the sensitive electrode material CoTiO3The device fabrication process was the same as in example 1.
Example 4:
the sensors were connected to a Rigol signal tester, and voltage signal tests were carried out by placing the sensors in an atmosphere of air, 500ppb acetylene, 1ppm acetylene, 2ppm acetylene, 5ppm acetylene, 10ppm acetylene, 20ppm acetylene, 50ppm acetylene, and 100ppm acetylene, respectively. The magnitude of the response value of the device is represented by Δ V (potential difference between the reference electrode and the sensitive electrode), and its value is VGas to be measured-VAir (a). The specific method comprises the following steps:
1. the sensor is connected to a Rigol signal tester, and the device is placed in a test bottle filled with air and having a volume of 1L to achieve stability, namely the electromotive force value (V) of the device in the airAir (a))。
2. Rapidly transferring the sensor to a container containing a concentration C to be measured2H2In a test bottle of gas until the response signal is stabilized, i.e. the device is in C2H2Electromotive force value (V) ofC2H2)。
3. And transferring the device back to the empty gas cylinder until the device is stable, and finishing a response recovery process by the device. The device is in C2H2And the difference in electromotive force in the air (Δ V ═ V)C2H2-VAir (a)) I.e. the device is aligned to the concentration C2H2The response value of (2). The sensor is fixedThe sensitivity of the sensor is determined by measuring the slope of the linear relationship between the response value and the corresponding concentration logarithm in the concentration range.
Table 1: with CdTiO3、NiTiO3、CoTiO3Sensor pair as sensitive electrode material 100ppm C2H2And comparing the response values.
Table 2: with CdTiO3Data on the variation of Δ V with acetylene concentration for a sensor that is a sensitive electrode material
| Concentration of acetylene (ppm) | Potential difference between sensing electrode and reference electrode delta V (mV) |
| 0.5 | -1 |
| 1 | -2.3 |
| 2 | -4 |
| 5 | -9 |
| Sensitivity (mV/decade) | -8 |
| 5 | -9 |
| 10 | -21.5 |
| 20 | -47 |
| 50 | -85.5 |
| 100 | -126 |
| Sensitivity (mV/decade) | -91 |
In Table 1, CdTiO is shown3、NiTiO3、CoTiO3The sensor which is a sensitive electrode material has a response value of 100ppm acetylene. As can be seen from the table, the use of CdTiO3The response value of the device which is the sensitive electrode material is the highest and is-126 mV. In addition, as can be seen from Table 2, CdTiO3The lower limit of detection of the device on acetylene reaches 500 ppb. The sensitivity to acetylene of 0.5-5 ppm and 5-100 ppm is-8 mV/decade and-91 mV/decade. Therefore, the mixed potential type sensor constructed at present has good sensitivity to acetylene, and has good potential application prospect in the field of atmospheric environment detection.
Claims (2)
1. Based on YSZ and MTiO3The mixed potential type acetylene sensor with the sensitive electrode is characterized in that: from bottom to top in turn by Al with Pt heating electrode2O3The ceramic plate, the YSZ substrate, the strip Pt reference electrode and the strip sensitive electrode; the Pt reference electrode and the sensitive electrode are separately and symmetrically arranged at two ends of the upper surface of the YSZ substrate, the lower surface of the YSZ substrate and the Al with the Pt heating electrode2O3One surface of the Pt heating electrode of the ceramic plate is bonded together; the sensitive electrode material is MTiO3M is Cd, Ni or Co, sensitive electrode material MTiO3Is prepared by the following method of preparation,
mixing M (NO)3)2·nH2Dissolving O in ethanol, and stirring at room temperature until the O is dissolved; adding tetrabutyl titanate into the solution, continuously stirring uniformly, adding citric acid and water, stirring at room temperature to form uniform sol, and standing for 20-30 hours to obtain gel; m (NO)3)2·nH2The molar ratio of the used O, tetrabutyl titanate and citric acid is 1: 1: 2; drying the obtained gel for 12-24 hours at 80-90 ℃ under a vacuum condition to obtain dry gel, and finally sintering the dry gel for 1-3 hours at 900-1100 ℃ to obtain MTiO3And (3) sensitive electrode material.
2. A YSZ and MTiO based alloy according to claim 13The preparation method of the mixed potential type acetylene sensor with the sensitive electrode comprises the following steps:
(1) manufacturing a Pt reference electrode: manufacturing a strip-shaped Pt reference electrode with the thickness of 15-20 microns at one end of the upper surface of the YSZ substrate by using Pt slurry, folding a Pt wire, adhering the Pt wire to the middle position of the reference electrode to be used as an electrode lead, baking the YSZ substrate at 90-120 ℃ for 1-2 hours, sintering the YSZ substrate at 1000-1100 ℃ for 1-2 hours, removing terpineol in the Pt slurry, and cooling to room temperature;
(2) preparation of MTiO3A sensitive electrode: mixing MTiO3The sensitive electrode material is mixed into slurry with deionized water, and the mass concentration is 2-20%; by MTiO3Preparing a strip-shaped sensitive electrode with the thickness of 20-30 microns at the other end of the upper surface of the YSZ substrate, which is symmetrical to the reference electrode, of the slurry, and folding a platinum wire in half and then adhering the platinum wire to the middle position of the sensitive electrode to be used as an electrode lead;
(3) sintering the YSZ substrate with the reference electrode and the sensitive electrode prepared in the step (2) at 800-1000 ℃ for 1-3 hours;
(4) preparing an inorganic adhesive by measuring 2-4 m L sodium silicate Na2SiO3·9H2O, and is called Al2O30.7-1.0 g powder, mixing water glass and Al2O3Mixing the powders, and stirring to obtain inorganic adhesiveA mixture;
(5) using inorganic adhesive to make the lower surface of YSZ substrate and Al with Pt heating electrode2O3One surface of the Pt heating electrode of the ceramic plate is bonded together;
(6) welding and packaging the device obtained in the step (5) to obtain the product based on YSZ and MTiO3The mixed potential type acetylene sensor with sensitive electrodes.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| RU2194975C2 (en) * | 2001-01-15 | 2002-12-20 | Михайлова Антонина Михайловна | Solid-state electrochemical gas analyzer for finding-out acetylene |
| CN109946358A (en) * | 2019-03-29 | 2019-06-28 | 吉林大学 | One kind is with MTiO3Electric potential type SO is blended together for the YSZ base of sensitive electrode2Sensor, preparation method and applications |
| CN109946363A (en) * | 2019-04-02 | 2019-06-28 | 吉林大学 | One kind is based on the porous SnO that classifies2/Zn2SnO4The C of sensitive electrode2H2Sensor and preparation method thereof |
| CN110455889A (en) * | 2019-08-14 | 2019-11-15 | 吉林大学 | Based on YSZ and NiTiO3Sensitive electrode blendes together electric potential type acetaldehyde sensor and preparation method thereof |
-
2020
- 2020-04-09 CN CN202010271374.2A patent/CN111413386A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| RU2194975C2 (en) * | 2001-01-15 | 2002-12-20 | Михайлова Антонина Михайловна | Solid-state electrochemical gas analyzer for finding-out acetylene |
| CN109946358A (en) * | 2019-03-29 | 2019-06-28 | 吉林大学 | One kind is with MTiO3Electric potential type SO is blended together for the YSZ base of sensitive electrode2Sensor, preparation method and applications |
| CN109946363A (en) * | 2019-04-02 | 2019-06-28 | 吉林大学 | One kind is based on the porous SnO that classifies2/Zn2SnO4The C of sensitive electrode2H2Sensor and preparation method thereof |
| CN110455889A (en) * | 2019-08-14 | 2019-11-15 | 吉林大学 | Based on YSZ and NiTiO3Sensitive electrode blendes together electric potential type acetaldehyde sensor and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| CAILENG WANG 等: "YSZ-based mixed-potential type highly sensitive acetylene sensor based on porous SnO2/ZnSnO4 as sensing electrode" * |
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