CN116046854A - Gas-sensitive composite material, preparation method and sensor - Google Patents
Gas-sensitive composite material, preparation method and sensor Download PDFInfo
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- CN116046854A CN116046854A CN202310160232.2A CN202310160232A CN116046854A CN 116046854 A CN116046854 A CN 116046854A CN 202310160232 A CN202310160232 A CN 202310160232A CN 116046854 A CN116046854 A CN 116046854A
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- G01N27/04—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating impedance by investigating resistance
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Abstract
The invention belongs to the technical field of sealing composite materials, and particularly relates to a gas-sensitive composite material, which is characterized in that a nano-scale fiber sheet shape of a zinc oxide nano-scale fiber material is matched with a platinum element doped with a specific proportion on the basis of zinc oxide, so that oxygen vacancies and active sites on the surface of the zinc oxide are correspondingly increased, the surface adsorption-desorption process of gas molecules is accelerated, the contact barrier height is reduced, and methane gas in a transformer can be responded rapidly. The molecular sieve material is coated on the zinc oxide nano-scale fiber material, so that the interference of carbon monoxide gas on response can be reduced, the transformer gas leakage fault can be accurately monitored, the complex internal gas environment of the transformer can be treated, and the method is suitable for fault monitoring of the power transformer.
Description
Technical Field
The invention belongs to the technical field of gas sensing, and particularly discloses a gas-sensitive composite material, a preparation method thereof and a sensor using the gas-sensitive composite material.
Background
With the development of ultra-high voltage and ultra-high voltage power transmission and transformation engineering, the number and capacity of power transformers of various voltage classes are rapidly increased. Power transformers are essential electrical devices whose operating conditions directly affect the safety and reliability of the power system. The fault of the power transformer brings huge economic loss to the national economy of China.
At present, most of large power transformers adopt an oilpaper insulation structure. When the transformer suffers from an internal insulation failure, the transformer may generate some low molecular hydrocarbon gas, such as methane (CH) 4 ) Ethane (C) 2 H 6 ) Ethylene (C) 2 H 4 ) Acetylene (C) 2 H 2 ) And the like, these gas components are mostly dissolved in transformer oil. On-line monitoring of the component content of these dissolved hydrocarbon gases and their rate of formation is one of the most effective and convenient methods of diagnosing incipient faults in transformers. This approach can distinguish between different types of faults occurring in the power transformer, such as overheating, partial discharge, spark discharge, and arc discharge.
Gas sensing technology is the core of online monitoring. Currently, semiconductor gas sensors, field effect transistors, catalytic combustion sensors, fuel cell sensors, and optical sensors are methods used mainly to detect characteristic fault gases. The metal oxide semiconductor material has been valued by science and technology for many years because of its remarkable advantages of simple manufacturing process, low maintenance cost, fast reaction and recovery time, long service life, etc., and is widely used for detecting flammable, explosive and toxic gases. However, the general metal oxide sensor is insensitive to the response of certain detected gases or has poor adaptability to the detection environment, and can be used only in a narrow temperature range; and the transformer can generate various gases when in fault, and part of the gases can interfere with the gases to be detected, so that the detection result is misaligned or the response to certain gases to be detected is insensitive in a specific environment, and the detection purpose cannot be achieved.
Disclosure of Invention
In order to solve the technical problems listed in the background art, the invention provides a gas-sensitive composite material, which comprises a ceramic substrate, a gas-sensitive layer and a coating film which are sequentially attached from inside to outside, and is characterized in that: the gas-sensitive layer is made of zinc oxide nano-scale sheet material doped with 1% Pt, and the component of the coating film is AX-21 molecular sieve.
Preferably, the preparation flow of the zinc oxide nanoscale sheet material comprises the following steps: zinc acetate and CTAB (cetyltrimethylammonium bromide) are added into ethanol and stirred uniformly, and then 1% platinum chlorate solution is added; adding sodium hydroxide into the solution until the PH value is 13, and stirring for half an hour; the solution is subjected to heat preservation for 8 hours at 200 ℃, and is prepared after centrifugation and drying.
The invention also provides a preparation method of the gas-sensitive composite material, which comprises the following specific steps:
adding a zinc oxide nanoscale sheet material doped with 1% Pt into an organic solvent, grinding uniformly in a mortar, coating on the surface of a ceramic substrate, putting into a muffle furnace, heating to 350 ℃ at a speed of 1 ℃/min, maintaining for 3 hours to form a gas-sensitive layer, and coating an AX-21 molecular sieve material on the surface of the gas-sensitive layer in the same way.
Preferably, the preparation flow of the zinc oxide nanoscale sheet material comprises the following steps: zinc acetate and CTAB are added into ethanol and stirred uniformly, and then 1% platinum chlorate solution is added; adding sodium hydroxide into the solution until the PH value is 13, and stirring for half an hour; the solution is subjected to heat preservation for 8 hours at 200 ℃, and is prepared after centrifugation and drying.
Preferably, the organic solvent is at least one of ethanol and water.
The invention also provides a sensor which uses the gas-sensitive composite material or the gas-sensitive composite material prepared by the preparation method.
Compared with the prior art, the invention has the following beneficial effects:
the zinc oxide nano-scale fiber material has a nano-scale fiber sheet shape, is doped with platinum element in a specific proportion on the basis of zinc oxide, so that oxygen vacancies and active sites on the surface of the zinc oxide are correspondingly increased, the surface adsorption-desorption process of gas molecules is accelerated, the contact barrier height is reduced, methane gas in a transformer can be responded rapidly, and the response is sensitive and has a high response value. The molecular sieve material is coated on the zinc oxide nano-scale fiber material, so that the interference of carbon monoxide gas on response can be reduced, the gas leakage fault of the transformer can be accurately monitored, and the complex internal gas environment of the transformer can be treated.
Drawings
FIG. 1 is an SEM image of Pt/ZnO and AX-21 molecular sieve material in an embodiment of the invention;
wherein the left graph is Pt/ZnO material, and the right graph is AX-21 molecular sieve material;
FIG. 2 is a graph of test results of a gas sensor without molecular sieve coating in accordance with the present invention for methane gas of different concentrations;
FIG. 3 is a graph showing the results of testing a gas sensor without molecular sieve coating for different concentrations of carbon monoxide gas in accordance with the present invention;
FIG. 4 is a graph of test results of a Pt/ZnO gas sensor coated with a molecular sieve against methane gas of different concentrations;
FIG. 5 is a graph of test results of a Pt/ZnO gas sensor coated with a molecular sieve for different concentrations of carbon monoxide gas;
fig. 6 is a graph of test results of a Pt/ZnO gas sensor coated with molecular sieve on methane and carbon monoxide mixed gas.
Detailed Description
The present invention will be described with reference to the drawings and the embodiments thereof, in order to make the objects, technical solutions and advantages of the present invention more apparent. It will be apparent that the described embodiments are only some, but not all, embodiments of the invention. Based on this embodiment, all other embodiments that a person of ordinary skill in the art would obtain without making any inventive effort are within the scope of the invention.
A preparation method of a gas-sensitive composite material and an embodiment of the obtained gas-sensitive composite material:
adding a proper amount of zinc acetate and CTAB into 80ml of ethanol, and stirring to prepare a mixed precursor solution;
adding 1% platinum chlorate solution;
adding sodium hydroxide into the solution until the PH value is 13, and stirring for half an hour;
and (3) preserving the temperature of the solution at 200 ℃ for 8 hours, and centrifuging and drying to obtain the Pt-doped zinc oxide nanoscale sheet material.
According to the preparation method, the zinc oxide nanoscale sheet material is prepared by a hydrothermal method, the nanoscale sheet material can be prepared, the oxygen vacancies and active sites on the surface of zinc oxide are correspondingly increased by doping the specific material form with platinum, the surface adsorption-desorption process of gas molecules is accelerated, the contact barrier height is reduced, the response to the methane gas leaked from the transformer can be faster, the response is sensitive, and the fault of the transformer is monitored accurately in real time. Meanwhile, the preparation method has simple steps and low cost, and is beneficial to industrialized mass production.
The method is favorable for forming a specific porous nanofiber structure by reasonably controlling the steps, so that the finally prepared nanofiber has extremely large specific surface area and higher gas sensitivity.
The standby AX-21 molecular sieve material and the nanoscale sheet material are observed under a scanning electron microscope, compared with the figure 1, and the preparation of the coating material is completed after the confirmation.
Pretreatment of ceramic electrode plates: the electrode plate is placed in ethanol solution, ultrasonic treatment is carried out for 10-15 minutes, then the electrode plate is transferred into deionized water, ultrasonic treatment is carried out for 10-15 minutes again, and drying is carried out at a proper temperature, wherein the treatment is to remove impurities such as dust, oil stains and the like attached to the electrode plate, keep the surface clean, and facilitate the subsequent coating of a gas-sensitive material layer.
Coating a gas-sensitive layer on the electrode sheet: and (3) taking a proper amount of powder of the zinc oxide nanoscale sheet material in a mortar, adding a proper amount of organic solvent for dissolution, grinding uniformly, sucking the solution by using a liquid-transferring gun, dripping the solution on the electrode sheet to form a layer of uniform gas-sensitive material film covering the electrode sheet, standing for a period of time, drying, transferring the electrode sheet into a muffle furnace, preserving the temperature at 350 ℃ for three hours, and taking out the electrode sheet after cooling to room temperature along with the furnace at a heating rate of 1 ℃/min.
Coating a molecular sieve on the gas-sensitive layer: adding a proper amount of AX-21 molecular sieve powder into a mortar, adding a proper amount of organic solvent for dissolution, grinding uniformly, sucking the solution by using a liquid-transferring gun, dripping the solution onto the electrode plate to form a layer of uniform film covering a gas-sensitive material film, standing for a period of time, drying, transferring the electrode plate into a muffle furnace, preserving heat at 350 ℃ for three hours, cooling to room temperature along with the furnace at a heating rate of 1 ℃/min, and welding on a base to obtain the required gas-sensitive material, wherein the gas-sensitive material consists of a ceramic substrate, a gas-sensitive layer and an AX-21 molecular sieve coating film from inside to outside.
Another embodiment of the present invention can be obtained by packaging the above gas-sensitive sensing material and welding a signal transmission line: a sensor; the methane gas is detected by the sensor as follows:
connecting the components with a gas measuring platform, applying 5V voltage to each component, setting a ventilation program, introducing test gas after introducing dry air for a period of time, and circularly and repeatedly detecting the test gas with different concentrations.
The resistance of the gas-sensitive material layer is measured through an external circuit, the stable basic resistance of the gas-sensitive sensor after the dry air is introduced for a period of time is marked as RO, the maximum resistance after the test gas is introduced is marked as Rg, and the gas response of the gas-sensitive sensor is calculated by the formula R=RO/Rg-1. The test results are shown in fig. 4-6.
Details of the test and comparison with the sensor without molecular sieve coating are as follows:
the test results of the Pt/ZnO sensor without molecular sieve coating for methane at different concentrations are shown in fig. 2, and it can be seen that the Pt/ZnO sensor has a good response to methane at a lower concentration, and can reach a response of about 3 for methane at 5 ppm.
Fig. 3 shows the results of carbon monoxide tests of a Pt/ZnO sensor without molecular sieve coating for different concentrations, and it can be seen that the Pt/ZnO sensor also has a higher response to carbon monoxide at a lower concentration, and a response of about 1.8 to 5ppm co, which causes a larger interference with methane detection.
Fig. 4 shows the results of a molecular sieve coated Pt/ZnO sensor tested for different concentrations of methane, and it can be seen that the molecular sieve coated Pt/ZnO sensor also has a higher response to lower concentrations of methane, and still can maintain a response around 3 for 5ppm methane.
Fig. 5 shows the results of carbon monoxide testing at different concentrations for a Pt/ZnO sensor coated with a molecular sieve, and it can be seen that the response to carbon monoxide of the Pt/ZnO sensor coated with a molecular sieve is significantly reduced compared to that of a sensor without a molecular sieve, and the response to 5ppm co is only about 0.9, which achieves the effect of reducing carbon monoxide interference.
The test results of the molecular sieve coated Pt/ZnO sensor on methane and carbon monoxide mixed gas with different concentrations are shown in fig. 6, and the molecular sieve coated Pt/ZnO sensor has very high response to 5ppm methane and carbon monoxide mixed gas, which can reach about 7.5, so that the molecular sieve coated Pt/ZnO sensor has higher anti-interference capability and response capability in the actual transformer environment, and can effectively detect methane in the transformer environment.
In general, the method of the invention uses the gas sensor as a means for detecting methane gas, and the coating of the molecular sieve eliminates the interference of carbon monoxide gas, thus realizing rapid response to methane gas with lower concentration and monitoring the operation state of the transformer in real time. When the transformer fails, an early warning is sent out, the methane leakage quantity can be judged, the working personnel can take corresponding countermeasures in time, and the occurrence of safety accidents is reduced. Meanwhile, the sensor adopts metal oxide as a sensitive material, so that the device has good time stability, and long-time accurate monitoring of methane gas is ensured. The gas sensor designed by the method has good detection effect, simple manufacturing method, low cost, good repeatability and long service life, and can realize mass industrialized production by magnetron sputtering after the gas sensitive material is made into the target material, thereby having good application prospect.
Finally, it should be noted that: the foregoing description is only a preferred embodiment of the present invention, and the present invention is not limited thereto, but it is to be understood that modifications and equivalents of some of the technical features described in the foregoing embodiments may be made by those skilled in the art, although the present invention has been described in detail with reference to the foregoing embodiments. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (7)
1. The utility model provides a gas-sensitive composite, includes ceramic substrate, gas-sensitive layer and coating film that from inside to outside laminating in proper order, its characterized in that: the gas-sensitive layer is made of zinc oxide nano-scale sheet material doped with 1% Pt, and the component of the coating film is AX-21 molecular sieve.
2. A gas sensitive composite material according to claim 1, characterized in that: the preparation process of the zinc oxide nanoscale sheet material comprises the following steps: zinc acetate and CTAB are added into ethanol and stirred uniformly, and then 1% platinum chlorate solution is added; adding sodium hydroxide into the solution until the PH value is 13, and stirring for half an hour; the solution is subjected to heat preservation for 8 hours at 200 ℃, and is prepared after centrifugation and drying.
3. The preparation method of the gas-sensitive composite material is characterized by comprising the following steps of:
adding a zinc oxide nanoscale sheet material doped with 1% Pt into an organic solvent, grinding uniformly in a mortar, coating on the surface of a ceramic substrate, putting into a muffle furnace, heating to 350 ℃ at a speed of 1 ℃/min, maintaining for 3 hours to form a gas-sensitive layer, and coating an AX-21 molecular sieve material on the surface of the gas-sensitive layer in the same way.
4. A method for preparing a gas-sensitive composite material as claimed in claim 3, wherein the preparation process of the zinc oxide nano-scale sheet material comprises the following steps: zinc acetate and CTAB are added into ethanol and stirred uniformly, and then 1% platinum chlorate solution is added; adding sodium hydroxide into the solution until the PH value is 13, and stirring for half an hour; the solution is subjected to heat preservation for 8 hours at 200 ℃, and is prepared after centrifugation and drying.
5. The method of producing a gas-sensitive composite material as claimed in claim 4, wherein the organic solvent is at least one of ethanol and water.
6. A sensor comprising the gas sensitive composite of any one of claims 1 or 2.
7. A sensor comprising a gas sensitive composite made by the method of making a gas sensitive composite of any one of claims 3-5.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116626114A (en) * | 2023-07-25 | 2023-08-22 | 南方电网数字电网研究院有限公司 | C 2 H 6 Sensor, preparation method, gas detection device and application |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116626114A (en) * | 2023-07-25 | 2023-08-22 | 南方电网数字电网研究院有限公司 | C 2 H 6 Sensor, preparation method, gas detection device and application |
| CN116626114B (en) * | 2023-07-25 | 2023-10-20 | 南方电网数字电网研究院有限公司 | C 2 H 6 Sensor, preparation method, gas detection device and application |
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