CN113219010A - Ethanol sensor of ZnO double-shell hollow structure microsphere sensitive material and preparation - Google Patents

Ethanol sensor of ZnO double-shell hollow structure microsphere sensitive material and preparation Download PDF

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CN113219010A
CN113219010A CN202110543850.6A CN202110543850A CN113219010A CN 113219010 A CN113219010 A CN 113219010A CN 202110543850 A CN202110543850 A CN 202110543850A CN 113219010 A CN113219010 A CN 113219010A
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ethanol
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孙鹏
姜滨
卢革宇
刘方猛
王晨光
刘晓敏
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Jilin University
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Abstract

一种基于ZnO双壳空心结构微球敏感材料的乙醇传感器、制备方法及其在检测乙醇蒸汽中的应用,属于半导体氧化物气体传感器技术领域。由外表面带有两条平行、环状且彼此分立的金电极的Al2O3陶瓷管衬底、涂覆在Al2O3陶瓷管外表面和金电极上的ZnO双壳空心结构微球敏感材料、置于Al2O3陶瓷管内的镍铬加热线圈组成。本发明利用内部中空、结构疏松、尺寸均一的ZnO双壳空心结构微球开发出了具有高性能的乙醇气体传感器。传感器检测下限可以达到1ppm。此外,本发明器件工艺简单、体积小、成本低廉、适于大批量生产,因而在检测乙醇气体含量方面有广阔的应用前景。

Figure 202110543850

An ethanol sensor based on a ZnO double-shell hollow structure microsphere sensitive material, a preparation method and an application in detecting ethanol vapor belong to the technical field of semiconductor oxide gas sensors. Al 2 O 3 ceramic tube substrate with two parallel, annular and separated gold electrodes on the outer surface, ZnO double-shell hollow structure microspheres coated on the outer surface of Al 2 O 3 ceramic tube and gold electrodes Sensitive materials, nickel-chromium heating coils placed in Al 2 O 3 ceramic tubes. The invention develops a high-performance ethanol gas sensor by utilizing the ZnO double-shell hollow structure microspheres with hollow interior, loose structure and uniform size. The detection limit of the sensor can reach 1ppm. In addition, the device of the invention has simple process, small volume, low cost, and is suitable for mass production, so it has broad application prospects in detecting the content of ethanol gas.

Figure 202110543850

Description

Ethanol sensor of ZnO double-shell hollow structure microsphere sensitive material and preparation
Technical Field
The invention belongs to the technical field of semiconductor oxide gas sensors, and particularly relates to an ethanol sensor based on a ZnO double-shell hollow-structure microsphere sensitive material, a preparation method and application of the ethanol sensor in detection of ethanol steam.
Background
The harm of ethanol to the human body is mainly manifested as an inhibitory effect on the central nervous system, first causing excitation and then inhibition. Acute poisoning can be divided into four stages of excitation, hypnosis, anesthesia and asphyxia. Prolonged exposure to high concentrations of ethanol can cause irritation symptoms in the nasal and ocular mucosae, as well as headache, dizziness, fatigue, nausea, and the like. In addition, the harmfulness of drunk driving is extremely high, according to the threshold values of the blood and breath alcohol content of vehicle drivers and the inspection standard (GB/T19522-2010) of the people's republic of China, the breath alcohol concentration is 20-80 mg/100mL (44-176 ppm), namely the drunk driving concentration, and the breath alcohol concentration is more than 80mg/100mL, and belongs to the drunk driving concentration. The sensor is widely concerned and applied as a means for acquiring information, so that the research and development of the ethanol gas sensor with high gas-sensitive response and low detection lower limit is of great significance.
In fact, research surrounding the improvement of the sensitivity of the oxide semiconductor sensor is continuously deepened, and especially the development of the nano scientific technology provides good opportunities for improving the performance of the sensor. Research shows that the recognition function, the conversion function and the utilization rate of a sensitive body of the gas sensitive material determine the sensitivity degree of the oxide semiconductor sensor. Through research, the sensitivity and selectivity of the sensor can be remarkably improved by synthesizing the semiconductor oxide material with a hollow structure. This is mainly because the hollow structure material can improve the utilization rate of the sensitive body by promoting the diffusion of gas molecules into the sensitive layer. Based on this, the development of the design and preparation of the hollow-structure semiconductor oxide has important significance for improving the performance of the gas sensor and expanding the application of the gas sensor.
Disclosure of Invention
The invention aims to provide an ethanol sensor based on a ZnO double-shell hollow-structure microsphere sensitive material, a preparation method and application of the ethanol sensor in the aspect of detecting ethanol steam in the environment. The invention increases the sensitivity of the sensor and reduces the detection lower limit of the sensor by adjusting the microstructure of the semiconductor material, thereby promoting the practicability of the sensor in the field of gas detection.
The sensor obtained by the invention has higher sensitivity, better selectivity and lower detection lower limit. The lower detection limit of the sensor is 1ppm, and the sensor can be used for detecting the content of ethanol vapor in the environment. The sensor with the tubular structure is simple in manufacturing process, small in size, low in price and beneficial to industrial mass production, so that the sensor has important application value.
The ethanol sensor based on the ZnO double-shell hollow-structure microsphere sensitive material comprises Al with two parallel, annular and mutually-separated gold electrodes on the outer surface2O3Ceramic tube substrate coated with Al2O3The nano sensitive material on the outer surface of the ceramic tube and the gold electrode is arranged on the Al2O3A nichrome heating coil in the ceramic tube; the method is characterized in that: the nano sensitive material is loose ZnO double-shell hollow structure microspheres and is prepared by the following steps:
(1) firstly, 0.50-0.65 g of Zn (NO)3)2·6H2Dissolving O, 0.4-0.6 g of urea and 0.1-0.2 g of potassium citrate monohydrate in 90-110 mL of deionized water, and fully stirring for 20-40 min;
(2) putting the uniform transparent solution obtained in the step (1) into a beaker, carrying out coprecipitation reaction for 3-5 h at 95-115 ℃, cooling to room temperature, and then carrying out coprecipitation reaction for 3-5 h at 105-125 ℃ on the beaker;
(3) and (3) after the reaction in the step (2) is finished and the temperature is reduced to room temperature, alternately centrifuging and washing the obtained white precipitate for 4-8 times by using deionized water and absolute ethyl alcohol, drying the washed white precipitate at 70-90 ℃ for 10-15 h, and calcining at 450-550 ℃ for 0.5-1.5 h to obtain white powder of the microsphere sensitive material with the ZnO double-shell hollow structure.
Al2O3The inner diameter of the ceramic tube is 0.7-0.9 mm, the outer diameter is 1.1-1.3 mm, and the length is 3.8-4.2 m; the width of the gold electrode is 0.35-0.45 mm, the distance between the two gold electrodes is 0.4-0.6 mm, 2 platinum wire leads are led out of each gold electrode, and the length of each gold electrode is 4-6 mm.
The invention relates to a preparation method of an ethanol sensor based on a ZnO double-shell hollow structure microsphere sensitive material, which comprises the following steps:
(1) uniformly mixing 5-15 mg of calcined white ZnO double-shell hollow-structure microsphere sensitive material powder with 0.1mL of a mixed solvent of absolute ethyl alcohol (absolute ethyl alcohol being more than or equal to 99.7%) and deionized water (the volume ratio of the absolute ethyl alcohol to the deionized water is 1:1) to form slurry, dipping the slurry by using a brush, and coating the slurry on Al2O3The outer surface of the ceramic tube substrate and the two parallel, annular and mutually-separated gold electrodes are provided, and the thickness of the sensitive material is 15-30 mu m;
(2) coated Al2O3Calcining the ceramic tube at 450-550 ℃ for 0.5-1.5 h, and then enabling a nichrome heating coil (with the number of turns of 50-60) with the resistance value of 30-40 omega to penetrate through Al2O3In the ceramic tube, the current passing through the heating coil is controlled to provide the proper working temperature of the sensor, and finally four platinum wire leads of the sensor and two ends of the nichrome heating coil are welded on the indirectly heated hexagonal tube seat;
(3) and (3) aging the sensor in the step (2) in an air environment at 180-220 ℃ for 6-8 days to obtain the ethanol sensor based on the ZnO double-shell hollow-structure microsphere sensitive material.
The working principle is as follows:
when the ethanol sensor based on the microsphere sensitive material with the ZnO double-shell hollow structure is placed in the air, oxygen molecules in the air can take electrons from ZnO and take O2 -、O-Or O2-In the method (2), a depletion layer is formed on the surface of the material, and the resistance increases. When the sensor contacts ethanol gas at a certain proper temperature, ethanol gas molecules and adsorbed oxygen molecules generate oxidation-reduction reaction, and electrons are released back to ZnO, so that ZnOThe resistance drops. Here we define the sensitivity of the sensor as S: r ═ Sa/RgWherein R isaIs the resistance in air between the gold electrodes of the sensor, RgThe resistance of the gold electrode of the sensor after contacting with ethanol is shown.
The ethanol sensor based on the ZnO double-shell hollow structure microsphere sensitive material prepared by the invention has the following advantages:
1. the ZnO double-shell hollow structure can be synthesized by a simple coprecipitation method, and the synthesis method is simple and low in cost;
2. by regulating the internal structure of ZnO, the sensitivity to ethanol is improved, the lower limit of detection of the material is low, and the method has a wide application prospect in the aspect of content detection;
3. the tube sensor is commercially available, and the device has simple process and small volume and is suitable for mass production.
Drawings
FIG. 1: a structural schematic diagram of the ZnO double-shell hollow structure microsphere ethanol sensor; FIG. 1(a) is a sectional view, and FIG. 1(b) is a schematic view showing a welded state
FIG. 2: scanning electron micrographs and transmission electron micrographs of the sensitive materials prepared in comparative example, example 1 and example 2.
FIG. 3: comparative, example 1 and example 2 are graphs comparing sensitivity at 275 c to 100ppm of 5 different gases.
FIG. 4: sensitivity versus operating temperature for the comparative, example 1 and example 2 ethanol gas at 100 ppm.
FIG. 5: example 4 sensitivity curves for different concentrations of ethanol gas at the optimum operating temperature; FIG. 5(a) is a graph showing real-time sensitivity curves for ethanol gas at different concentrations; FIG. 5(b) is a graph showing the sensitivity of the gas sensor to ethanol gas of different concentrations.
As shown in fig. 1, the names of the respective components are: annular gold electrode 1, Al2O3An insulating ceramic tube 2, a ZnO double-shell hollow structure microsphere sensitive material 3, a nickel-chromium alloy heating coil 4, a platinum wire 5 and an indirectly heated hexagonal tube seat 6;
FIG. 2 is a scanning electron microscope (a, b, c, d, e, f, g, h, i) photograph and a transmission electron microscope (j, k) photograph of the sensitive materials prepared in comparative example, example 1 and example 2. As can be seen from the figure, the sensitive material of the comparative example corresponding to FIGS. 2a, b and c is a solid sphere structure, the size of the solid microspheres is about 1.5-2 μm, the sensitive material of the example 1 corresponding to FIGS. 2d, e and f is a core-shell sphere structure, the size of the microsphere structure is about 1.5-2 μm, and the sensitive material of the example 2 corresponding to FIGS. 2g, h and i is a double-shell hollow sphere structure, and the size of the microsphere structure is about 1.5-2 μm. In the experiment, three structures of a ZnO solid sphere, a ZnO core-shell sphere and a ZnO double-shell hollow sphere are synthesized by adjusting the temperature and the reaction time of the coprecipitation reaction. The specific reaction mechanism is that the Ostwald curing process is regulated and controlled by adjusting the coprecipitation reaction temperature and time, the longer the reaction time is, the higher the reaction temperature is, the more durable and violent the Ostwald curing process is in a certain reaction temperature and time range, and finally, the regulation and control of solid, core-shell and double-shell hollow structures of the ZnO internal structure are realized through the Ostwald curing process. Fig. 2j shows the lattice spacing as the (100) crystal plane of the pure phase ZnO, and the diffraction ring of fig. 2k shows the material as polycrystalline.
FIG. 3 is a graph comparing the sensitivity of comparative example, example 1 and example 2 at 275 deg.C to 100ppm of 5 different gases. As can be seen from the figure, the sensitivity of the sensor to ethanol is gradually improved along with the hollowing of the internal structure of the ZnO microsphere, and the highest sensitivity is achieved in the ZnO double-shell hollow structure.
FIG. 4 is a plot of sensitivity versus operating temperature for comparative example, example 1, and example 2, for 100ppm ethanol gas. It can be seen from the figure that the optimum working temperature for both sets of samples of the example is 275 ℃. At 275 deg.C, the sensitivity of the comparative example was 10.1, the sensitivity of example 1 was 31.1, the sensitivity of example 2 was 54.4, and the sensitivity of example 2 was the highest, approximately 5.4 times the sensitivity of the comparative example. Therefore, the ethanol sensor with high sensitivity can be constructed by regulating and controlling the inner cavity structure of ZnO.
FIG. 5(a) is a graph showing the real-time sensitivity of the test in example 2 at the optimum operating temperature for different concentrations of ethanol gas, and it can be seen that the concentration of ethanol decreasesThe sensitivity gradually decreased and 1ppm of ethanol gas could be detected. FIG. 5(b) is a graph showing the sensitivity of example 2 to different concentrations of ethanol gas at the optimum operating temperature. The sensitivity test method comprises the following steps: firstly, putting a sensor into an air bottle with the volume of 1L, testing real-time resistance through a resistance meter connected with the sensor, and obtaining the resistance value of the sensor in the air, namely R when the resistance value tends to be stablea(ii) a Then, a microsyringe is used for injecting 1-100 ppm of ethanol into a 1L gas cylinder, and after the resistance value is stable, the resistance value of the sensor in ethanol with different concentrations, namely R, is obtained through measurementgAccording to the definition of sensitivity S, formula S ═ Ra/RgAnd calculating the sensitivity of the sensor under different ethanol concentrations to finally obtain a standard working curve of ethanol concentration-sensitivity. As can be seen from the graph, the lower limit of detection of the sensor of example 2 is 1ppm, and the sensitivity at this time is about 1.5.
In actual measurement, R can be measured by the methoda、RgAnd comparing the obtained sensitivity value with a standard working curve of ethanol concentration-sensitivity to obtain the ethanol content in the atmosphere, wherein the ethanol sensor can be well applied to the detection of ethanol gas in the environment due to the characteristic.
Detailed Description
Comparative example:
a coprecipitation method is used for preparing a ZnO solid ball structure material to prepare an indirectly heated ethanol sensor, and the specific preparation process comprises the following steps:
(1) first 0.595g Zn (NO) is added3)2·6H2Dissolving O, 0.48g of urea and 0.13g of potassium citrate monohydrate in 100mL of deionized water, and fully stirring for 30 min;
(2) putting the uniform and transparent solution into a 100mL beaker, putting the beaker into an oven for coprecipitation reaction, wherein the oven parameters are set as follows: 4h at 90 ℃;
(3) after the reaction is finished and the temperature is reduced to the room temperature, the obtained white precipitate is alternately centrifugally washed for 6 times by using deionized water and absolute ethyl alcohol, the parameters of the centrifugal machine are 8000r/min and 5min, the white precipitate which is washed clean is dried at the temperature of 80 ℃, the drying time is 12h, the dried white precipitate is calcined in a muffle furnace after the reaction is finished, and the parameters of the muffle furnace are set as follows: 500 ℃ for 1 h; obtaining white powder of the ZnO solid sphere structure microsphere sensitive material;
(4) mixing calcined 10mg white powder with 0.1mL mixed solvent (the volume ratio of absolute ethyl alcohol with the mass fraction of more than or equal to 99.7% to deionized water is 1:1) to form slurry, dipping the slurry with a brush, and coating the slurry on Al2O3The outer surface of the ceramic tube (the surface is provided with two parallel and annular gold electrodes which are separated from each other) leads the slurry to be completely and uniformly loaded on the outer surfaces of the gold electrodes and the ceramic tube, and the thickness is 25 mu m. Al (Al)2O3The inner diameter of the ceramic tube is 0.8mm, the outer diameter is 1.2mm, and the length is 4 mm; the width of the gold electrode is 0.4mm, and the distance between the two gold electrodes is 0.5 mm; 2 platinum wire leads are led out of each gold electrode, and the length of each platinum wire lead is 5 mm.
(5) The coated ceramic tube was placed in a muffle furnace with the parameters set to: 500 ℃ for 1h, and then a nichrome heating coil having a resistance value of 35 Ω (actually measured by a multimeter) was passed through the Al2O3And in the ceramic tube, the current passing through the heating coil is controlled to provide the proper working temperature of the sensor, and finally, four platinum wires of the sensor and two ends of the nichrome heating coil are welded on the indirectly heated hexagonal tube seat.
(6) And aging the manufactured sensor for 7 days in an air environment at 200 ℃ to finally obtain the ethanol gas sensor based on the ZnO solid sphere structure nano material.
Example 1:
a coprecipitation method is used for preparing a ZnO core-shell sphere structure material to prepare an indirectly heated ethanol sensor, and the specific preparation process comprises the following steps:
(1) first 0.595g Zn (NO) is added3)2·6H2Dissolving O, 0.48g of urea and 0.13g of potassium citrate monohydrate in 100mL of deionized water, and fully stirring for 30 min;
(2) putting the uniform and transparent solution into a 100mL beaker, putting the beaker into an oven for coprecipitation reaction, wherein the oven parameters are set as follows: 4h at 90 ℃; cooling to room temperature after the reaction is finished, and continuing heating, wherein the oven parameters are set as follows: at 100 ℃ for 4 h;
(3) after the reaction is finished and the temperature is reduced to the room temperature, the obtained white precipitate is alternately centrifugally washed for 6 times by using deionized water and absolute ethyl alcohol, the parameters of the centrifugal machine are 8000r/min and 5min, the white precipitate which is washed clean is dried at the temperature of 80 ℃, the drying time is 12h, the dried white precipitate is calcined in a muffle furnace after the reaction is finished, and the parameters of the muffle furnace are set as follows: 500 ℃ for 1 h; obtaining white powder of the ZnO core-shell sphere structure microsphere sensitive material;
(4) mixing calcined 10mg white powder with 0.1mL mixed solvent (the volume ratio of absolute ethyl alcohol with the mass fraction of more than or equal to 99.7% to deionized water is 1:1) to form slurry, dipping the slurry with a brush, and coating the slurry on Al2O3The outer surface of the ceramic tube (the surface is provided with two parallel and annular gold electrodes which are separated from each other) leads the slurry to be completely and uniformly loaded on the outer surfaces of the gold electrodes and the ceramic tube, and the thickness is 25 mu m. Al (Al)2O3The inner diameter of the ceramic tube is 0.8mm, the outer diameter is 1.2mm, and the length is 4 mm; the width of the gold electrode is 0.4mm, and the distance between the two gold electrodes is 0.5 mm; 2 platinum wire leads are led out of each gold electrode, and the length of each platinum wire lead is 5 mm.
(5) The coated ceramic tube was placed in a muffle furnace with the parameters set to: 500 ℃ for 1h, then a nichrome heating coil with a resistance value of 35 Ω (actually measured by a multimeter) was passed through the Al2O3And finally, welding four platinum wires of the sensor and two ends of the nickel-chromium alloy heating coil on the indirectly heated hexagonal tube seat.
(6) And aging the manufactured sensor for 7 days in an air environment at 200 ℃ to finally obtain the ethanol gas sensor based on the ZnO core-shell structure nano material.
Example 2:
a coprecipitation method is used for preparing a ZnO double-shell sphere hollow structure material to prepare an indirectly heated ethanol sensor, and the specific preparation process comprises the following steps:
(1) first 0.595g Zn (NO) is added3)2·6H2Dissolving O, 0.48g of urea and 0.13g of potassium citrate monohydrate in 100mL of deionized water, and fully stirring for 30 min;
(2) putting the uniform and transparent solution into a 100mL beaker, putting the beaker into an oven for coprecipitation reaction, wherein the oven parameters are set as follows: at 100 ℃ for 4 h; cooling to room temperature after the reaction is finished, and continuing heating, wherein the oven parameters are set as follows: 110 ℃ for 4 h; obtaining white powder of the ZnO double-shell sphere hollow structure microsphere sensitive material;
(3) after the reaction is finished and the temperature is reduced to the room temperature, the obtained white precipitate is alternately centrifugally washed for 6 times by using deionized water and absolute ethyl alcohol, the parameters of the centrifugal machine are 8000r/min and 5min, the white precipitate which is washed clean is dried at the temperature of 80 ℃, the drying time is 12h, the dried white precipitate is calcined in a muffle furnace after the reaction is finished, and the parameters of the muffle furnace are set as follows: 500 ℃ for 1 h;
(4) mixing calcined 10mg white powder with 0.1mL mixed solvent (the volume ratio of absolute ethyl alcohol with the mass fraction of more than or equal to 99.7% to deionized water is 1:1) to form slurry, dipping the slurry with a brush, and coating the slurry on Al2O3The outer surface of the ceramic tube (the surface is provided with two parallel and annular gold electrodes which are separated from each other) leads the slurry to be completely and uniformly loaded on the outer surfaces of the gold electrodes and the ceramic tube, and the thickness is 25 mu m. Al (Al)2O3The inner diameter of the ceramic tube is 0.8mm, the outer diameter is 1.2mm, and the length is 4 mm; the width of the gold electrode is 0.4mm, and the distance between the two gold electrodes is 0.5 mm; 2 platinum wire leads are led out of each gold electrode, and the length of each platinum wire lead is 5 mm.
(5) The coated ceramic tube was placed in a muffle furnace with the parameters set to: 500 ℃ for 1h, then a nichrome heating coil with a resistance value of 35 Ω (actually measured by a multimeter) was passed through the Al2O3And in the ceramic tube, the current passing through the heating coil is controlled to provide the proper working temperature of the sensor, and finally, four platinum wires of the sensor and two ends of the nichrome heating coil are welded on the indirectly heated hexagonal tube seat.
(6) And aging the manufactured sensor for 7 days in an air environment at 200 ℃ to finally obtain the ethanol gas sensor based on the ZnO double-shell hollow-structure nano material.

Claims (4)

1.一种基于ZnO双壳空心结构微球敏感材料的乙醇传感器,由外表面带有两条平行、环状且彼此分立的金电极的Al2O3陶瓷管衬底,涂覆在Al2O3陶瓷管外表面和金电极上的纳米敏感材料,置于Al2O3陶瓷管内的镍铬合金加热线圈组成;其特征在于:纳米敏感材料为疏松的ZnO双壳空心结构微球,且由如下步骤制备得到:1. An ethanol sensor based on a ZnO double-shell hollow structure microsphere sensitive material, which consists of an Al 2 O 3 ceramic tube substrate with two parallel, annular and separate gold electrodes on the outer surface, coated on Al 2 The nano-sensitive material on the outer surface of the O 3 ceramic tube and the gold electrode is composed of a nickel-chromium alloy heating coil placed in the Al 2 O 3 ceramic tube; it is characterized in that: the nano-sensitive material is loose ZnO double-shell hollow structure microspheres, and Prepared by the following steps: (1)首先将0.50~0.65g Zn(NO3)2·6H2O、0.4~0.6g尿素、0.1~0.2g一水合柠檬酸钾溶解在90~110mL去离子水中并充分搅拌20~40min;(1) First, dissolve 0.50~0.65g Zn(NO 3 ) 2 ·6H 2 O, 0.4~0.6g urea, 0.1~0.2g potassium citrate monohydrate in 90~110mL deionized water and stir well for 20~40min; (2)将步骤(1)得到的均匀透明溶液放入烧杯中在95~115℃下共沉淀反应3~5h,冷却至室温后将烧杯再在105~125℃下共沉淀反应3~5h;(2) put the uniform and transparent solution obtained in step (1) into a beaker and conduct co-precipitation reaction at 95~115°C for 3~5h, and after cooling to room temperature, the beaker is then coprecipitated at 105~125°C for 3~5h; (3)步骤(2)的反应结束降至室温后,将所得白色沉淀用去离子水和无水乙醇交替离心洗涤4~8次,然后将洗涤干净的白色沉淀在70~90℃下烘干10~15h,再在450~550℃下煅烧0.5~1.5h,从而得到具有ZnO双壳空心结构微球敏感材料白色粉末。(3) After the reaction of step (2) is finished and lowered to room temperature, the obtained white precipitate is alternately centrifuged and washed with deionized water and absolute ethanol for 4 to 8 times, and then the washed white precipitate is dried at 70 to 90° C. 10 to 15 hours, and then calcined at 450 to 550° C. for 0.5 to 1.5 hours to obtain a white powder of the microsphere-sensitive material with a ZnO double-shell hollow structure. 2.如权利要求1所述的一种基于ZnO双壳空心结构微球敏感材料的乙醇传感器,其特征在于:Al2O3陶瓷管内径为0.7~0.9mm,外径为1.1~1.3mm,长度为3.8~4.2m;金电极的宽度0.35~0.45mm,两金电极的间距为0.4~0.6mm,每个金电极上引出2条铂丝导线,长度为4~6mm。2. The ethanol sensor based on ZnO double-shell hollow structure microsphere sensitive material as claimed in claim 1, characterized in that: the inner diameter of the Al 2 O 3 ceramic tube is 0.7-0.9 mm, and the outer diameter is 1.1-1.3 mm, The length is 3.8-4.2m; the width of the gold electrode is 0.35-0.45mm, the distance between the two gold electrodes is 0.4-0.6mm, and two platinum wire leads are drawn from each gold electrode, and the length is 4-6mm. 3.权利要求2所述的基于ZnO双壳空心结构微球敏感材料的乙醇传感器的制备方法,其步骤如下:3. the preparation method of the ethanol sensor based on ZnO double shell hollow structure microsphere sensitive material according to claim 2, its steps are as follows: (1)取5~15mg权利要求1煅烧后的ZnO双壳空心结构微球敏感材料白色粉末与0.1mL无水乙醇和去离子水的混合溶剂均匀混合形成浆料,无水乙醇与去离子水体积比为1:1;然后用毛刷蘸取浆料涂敷在Al2O3陶瓷管衬底外表面和两条平行、环状且彼此分立的金电极上,纳米敏感材料的厚度为15~30μm;(1) Take 5-15 mg of the white powder of the ZnO double-shell hollow structure microsphere sensitive material after calcination according to claim 1 and uniformly mix it with 0.1 mL of a mixed solvent of absolute ethanol and deionized water to form a slurry, anhydrous ethanol and deionized water The volume ratio is 1:1; then the slurry is dipped with a brush and coated on the outer surface of the Al 2 O 3 ceramic tube substrate and two parallel, annular and separate gold electrodes, and the thickness of the nano-sensitive material is 15 ~30μm; (2)将涂覆好的Al2O3陶瓷管在450~550℃下煅烧0.5~1.5h,然后将电阻值为30~40Ω的镍铬合金加热线圈穿过Al2O3陶瓷管内部,最后将四根铂丝导线以及镍铬合金加热线圈两端焊接到旁热式六角管座上;(2) The coated Al 2 O 3 ceramic tube is calcined at 450 to 550° C. for 0.5 to 1.5 hours, and then a nickel-chromium alloy heating coil with a resistance value of 30 to 40Ω is passed through the inside of the Al 2 O 3 ceramic tube, Finally, the four platinum wires and both ends of the nickel-chromium alloy heating coil are welded to the side-heated hexagonal socket; (3)将步骤(2)的传感器在180~220℃空气环境中老化6~8天,从而得到基于ZnO双壳空心结构微球敏感材料的乙醇传感器。(3) aging the sensor in step (2) in an air environment of 180-220° C. for 6-8 days, thereby obtaining an ethanol sensor based on a ZnO double-shell hollow structure microsphere sensitive material. 4.权利要求1或2所述的一种基于ZnO双壳空心结构微球敏感材料的乙醇传感器在在检测乙醇蒸汽中的应用。4. the application of a kind of ethanol sensor based on ZnO double shell hollow structure microsphere sensitive material described in claim 1 or 2 in detecting ethanol vapor.
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