CN112179957A - Perovskite-like gas-sensitive sensing material and preparation method of gas-sensitive sensor - Google Patents
Perovskite-like gas-sensitive sensing material and preparation method of gas-sensitive sensor Download PDFInfo
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- 238000010438 heat treatment Methods 0.000 claims description 46
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 26
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 23
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Abstract
The invention discloses a perovskite-like gas-sensitive sensing material and a preparation method of a gas-sensitive sensor, belonging to the technical field of gas-sensitive sensors. The gas-sensitive sensing material is Cs2PbI2(SCN)2(ii) a The working temperature of the gas-sensitive sensing material is 20-30 ℃; the gas-sensitive sensing material is suitable for ammonia NH3Acetone CH3COCH3Toluene C7H8Methanol CH3OH or ethanol C2H5And (5) OH. The perovskite-like gas-sensitive sensing material and the gas-sensitive sensor prepared by the invention can work at room temperature, and have higher sensitivity and better repeatability.
Description
Technical Field
The invention belongs to the technical field of gas sensors, and particularly relates to a perovskite-like gas-sensitive sensing material and a preparation method of a gas sensor.
Background
The gas sensor originally traced back to 1931, Braver discovered that the conductivity of CuO was accompanied by the absorption of water vaporBut is changed. Gas sensing research has turned to the practical device development stage beginning in the sixties of the twentieth century. In 1962, Seiyama et al first developed a gas sensor based on a ZnO semiconductor thin film and found that adsorption and desorption of gas at a certain temperature caused a change in resistance. Commercial SnO in 19682The gas sensor is put on the market, and then research on how to improve the gas sensing performance of the gas sensor becomes important.
The gas sensitive material is a main part of the gas sensor, and the gas sensor can be divided into a semiconductor sensor and a non-semiconductor sensor. Currently, SnO is widely used in domestic gas sensors2The semiconductor gas sensor is a main material and has the advantages of simple structure, convenient use, small volume, low energy consumption and the like. In addition, other materials such as Al2O3Quartz crystals and organic semiconductors also exhibit excellent gas sensing properties.
However, most gas sensors need to work at high temperature, and have very weak response and long response recovery time at room temperature. In 2014, Zhao et al discovered perovskite CH for the first time3NH3PbI3/TiO2When the film is exposed above the concentrated ammonia water, the color of the film is rapid<1s) change from brown to colorless, NH is removed3The original color is restored after the atmosphere, and the phenomenon shows CH3NH3PbI3The perovskite has the potential of being used as a sensitive material of a low-temperature gas sensor. Over the next few years, several studies have also shown that CH3NH3PbI3The material also produces a relatively sensitive response to other specific gases. Meanwhile, researchers have conducted intensive studies on perovskite gas sensors, including the use of different halogen elements for CH3NH3PbI3Partial substitution of iodine atom in (1), etc., and these materials are substituted for NH3、O3、NO2And acetone and the like exhibit good responsivity and high sensitivity. In addition, the gas sensor prepared by compounding the perovskite with the graphene or the nitrogen-doped carbon nanotube also shows higher responsivity.
However, the application of the organic-inorganic hybrid perovskite material is limited because the organic-inorganic hybrid perovskite material has poor stability and is very easy to decompose in a polar gas environment, and therefore, the research on various inorganic perovskite materials is carried out to find out an all-inorganic perovskite-like material Cs2PbI2(SCN)2The method has good response to ammonia gas, so that deep research is carried out.
Disclosure of Invention
In order to solve the problems, the invention provides a perovskite-like gas-sensitive sensing material which is Cs2PbI2(SCN)2(ii) a The working temperature of the gas-sensitive sensing material is 20-30 ℃; the gas-sensitive sensing material is suitable for ammonia NH3Acetone CH3COCH3Toluene C7H8Methanol CH3OH or ethanol C2H5OH。
The gas sensor prepared from the perovskite-like gas-sensitive sensing material comprises the gas-sensitive sensing material and an electrode for the gas-sensitive sensor, and the surface of the electrode for the gas-sensitive sensor is wrapped by the gas-sensitive sensing material.
The preparation method of the perovskite-like gas sensor specifically comprises the following steps:
1) preparation of Cs2PbI2(SCN)2A solution; cs2PbI2(SCN)2The concentration of the solution is 0.1-0.9 mmol/mL;
2) selecting a ceramic tube gold electrode with good wiring, and treating by adopting an ultraviolet ozone cleaning machine;
3) preheating the ceramic tube gold electrode obtained in the step 2);
4) dripping the solution obtained in the step 1) on the ceramic tube gold electrode obtained in the step 3) to enable the solution to completely wrap the ceramic tube gold electrode, and then carrying out heating annealing to prepare the inorganic material perovskite-like gas sensor.
The amount of the dripping solution in the step 4) is 1-5 mu L, the annealing temperature is 100-130 ℃, and the annealing time is 1-3 min.
Cs in step 1)2PbI2(SCN)2The specific preparation method of the solution comprises the following steps: dissolving cesium iodide and lead thiocyanate solids in an organic solvent, and heating, stirring and dissolving;
the mass ratio of cesium iodide to lead thiocyanate is 1:1-3: 1; the heating and stirring temperature is 60-70 ℃, and the heating and stirring time is 2-12 h;
the organic solvent is a mixed solution of N, N-dimethylformamide and dimethyl sulfoxide, and the volume ratio of the N, N-dimethylformamide to the dimethyl sulfoxide is 4:1-0: 1.
The treatment time in the step 2) is 10-20 min.
And 2) the ceramic tube gold electrode is a thin-wall ceramic tube, and the gold electrode and the platinum-iridium alloy lead are respectively arranged at two ends of the tube body.
In the step 3), the preheating temperature is 80-100 ℃, and the preheating time is 2-10 min.
Step 3) and step 4) are both carried out in a nitrogen glove box.
The invention has the beneficial effects that:
1. the invention adopts an all-inorganic perovskite-like material Cs2PbI2(SCN)2The gas sensor prepared by the method is used as a gas sensing material or a sensitive layer, has high sensitivity, can work under the conditions of 20-30 ℃, preferably 25 ℃, and has good stability and reusability because organic components are not contained.
Drawings
FIG. 1 is an XRD pattern of the material of example 1;
FIG. 2 is an SEM photograph of the surface material coated on the ceramic tube in example 1;
FIG. 3 shows a gas sensor pair NH in example 13The response graph of (a);
FIG. 4 shows the sensitivity of the gas sensor and NH in example 13A graph of concentration dependence;
FIG. 5 shows a gas sensor pair NH in example 13Response-recovery time map of (a);
FIG. 6 shows a gas sensor pair NH in example 13The detection limit map of (1);
FIG. 7 is a pair of gas sensors in example 2500ppm NH3A repeatability test chart of (1);
FIG. 8 is a graph showing the selectivity of the gas sensor in example 1 for different gases;
FIG. 9 is a schematic diagram of a ceramic tube gold electrode and a gas-sensitive sensing material, wherein 1-a thin-wall ceramic tube, 2-a platinum-iridium alloy wire, 3-a gold electrode, 4-a heating wire, and 5-a gas-sensitive sensing material.
Detailed Description
The invention is described in further detail below with reference to the following figures and specific examples:
the invention provides a perovskite-like gas-sensitive sensing material which is Cs2PbI2(SCN)2(ii) a The working temperature of the gas-sensitive sensing material is 20-30 ℃; the gas-sensitive sensing material is suitable for ammonia NH3Acetone CH3COCH3Toluene C7H8Methanol CH3OH or ethanol C2H5OH。
A gas sensor prepared from perovskite-like gas-sensitive sensing materials comprises the gas-sensitive sensing materials and electrodes for the gas-sensitive sensor, wherein the surfaces of the electrodes for the gas-sensitive sensor are wrapped by the gas-sensitive sensing materials.
The gas-sensitive sensing materials respectively react with ammonia NH with the concentration of 500ppm3Acetone CH3COCH3Toluene C7H8Methanol CH3OH, ethanol C2H5The sensitivity of OH was 5.152, 1.077, 1.09, 1.068, 1.04, respectively.
A preparation method of a perovskite-like gas sensor specifically comprises the following steps:
1) preparation of Cs2PbI2(SCN)2Solution, Cs2PbI2(SCN)2The concentration of the solution is 0.1-0.9 mmol/mL; cs2PbI2(SCN)2The solvent of the solution is an organic solvent, specifically a mixed solution of N, N-Dimethylformamide (DMF) and dimethyl sulfoxide (DMSO), and the volume ratio of the DMF to the DMSO is 4:1-0: 1;
Cs2PbI2(SCN)2the specific preparation method of the solution comprises the following steps: weighing iodinationCesium (CsI) and lead thiocyanate (Pb (SCN)2) Dissolving solid powder in an organic solvent, then placing the solution on a heating stirring table, and filtering the solution after complete dissolution for later use; cesium iodide (CsI) and lead thiocyanate (Pb (SCN)2) The mass ratio of the solid powder is 1:1-3: 1; the heating and stirring temperature is 60-70 ℃, and the heating and stirring time is 2-12 h.
2) Selecting a ceramic tube gold electrode with good wiring, and treating by adopting an ultraviolet ozone cleaning machine (UVO); the treatment time is 10-20 min; the gold electrode and Pt of the ceramic tube gold electrode are intact;
3) preheating the ceramic tube gold electrode obtained in the step 2); preheating at 80-100 deg.C for 2-10 min;
4) dripping the solution obtained in the step 1) on the ceramic tube gold electrode obtained in the step 3), and then placing the ceramic tube gold electrode on a heating table for heating and thermal annealing to obtain the perovskite-like gas-sensitive sensor made of the inorganic material; the amount of the dripping solution is 1-5 mu L, so that the solution can completely wrap the ceramic tube gold electrode, the thermal annealing temperature is 100-;
the inorganic perovskite gas-sensitive material is suitable for ammonia (NH)3) Acetone (CH)3COCH3) Toluene (C)7H8) Methanol (CH)3OH), ethanol (C)2H5OH)。
A perovskite-like gas sensor test procedure:
welding the perovskite-like gas sensor obtained in the step 4) on a hexagonal base, and then inserting the perovskite-like gas sensor on a test board of a test system. During testing, directly injecting gas with a determined volume into the testing box, and opening the fan to quickly and uniformly mix the gas with air; when the liquid vapor is tested, the required measured volume is calculated according to a calculation formula, the liquid vapor is injected onto an evaporation dish, heated and evaporated into a gaseous state, and the gaseous state is uniformly mixed by a fan. After the sensor detects the gas to be detected, the resistance change of the sensor or the voltage change of the load resistance is read through system processing.
The gas-sensitive test of the sensor adopts a WS-30B test system, wherein the liquid vapor is calculated by the formula
As shown in FIG. 9, the gold electrode of the ceramic tube according to the present invention is formed by disposing a gold electrode 3 and a platinum-iridium alloy wire 2 at each end of a thin-walled ceramic tube 1, and the electrodes can be replaced with other electrodes in the field of gas sensors. Preparing a gas-sensitive sensing material 5 on the surface of the ceramic tube gold electrode; the heating wire 4 is arranged in the diameter of the ceramic tube gold electrode to heat the ceramic tube gold electrode.
In the operation process of the invention, the steps except the preparation of the solution, the UVO treatment of the gold electrode of the ceramic tube and the test process of the gas sensor are all carried out in a nitrogen glove box.
The invention aims to provide a gas sensor which takes perovskite-like materials as a sensing layer of the gas sensor and can work at room temperature.
Example 1:
1) preparing a perovskite-like precursor solution: 0.6mmol of cesium iodide (CsI) and 0.3mmol of lead thiocyanate (Pb (SCN) were weighed out separately2) And dissolved in a mixed solution of 800mL of DMF and 200mL of DMSO, followed by stirring with heating on a stirring table at 60 ℃ for 2 hours to obtain 0.3mmol/mL of Cs2PbI2(SCN)2A solution;
cs at a concentration of 0.1mmol/mL to 0.9mmol/mL2PbI2(SCN)2In the solution, the responsivity increases along with the increase of the concentration from 0.1mmol/mL to 0.3 mmol/mL; from 0.3mmol/mL to 0.9mmol/mL, the responsivity decreases with increasing concentration, Cs2PbI2(SCN)2When the concentration of the precursor is 0.3mmol/mL, the best responsivity is obtained;
2) pretreating a ceramic tube gold electrode: selecting a ceramic tube gold electrode with a complete gold electrode and a complete Pt wire as shown in FIG. 9, and carrying out UVO treatment on the ceramic tube gold electrode for 20 min;
3) solution treatment and preheating of a ceramic tube gold electrode: the Cs obtained in the step 1) is treated2PbI2(SCN)2Transferring the solution and the ceramic tube gold electrode obtained in the step 2) into a nitrogen glove box, and filtering Cs by using a 0.22-micron filter head2PbI2(SCN)2Setting the two heating tables to be 80 ℃ and 120 ℃ respectively for standby, and placing two pieces of 1.5 cm-10 cm soda-lime glass on the two heating tables respectively, wherein the distance between the two pieces of soda-lime glass is about 2 cm;
4) preparation of gas-sensitive sensing material (perovskite-like layer): penetrating a graphite rod with the thickness of 0.5mm through a ceramic tube gold electrode, placing the ceramic tube gold electrode on a heating table with the temperature of 80 ℃, respectively placing two ends of the graphite rod on two pieces of soda-lime glass, preheating for 2min, measuring 3 mu L of solution by using a liquid transfer gun, dripping the solution on the ceramic tube gold electrode, sucking away the redundant solution on the ceramic tube gold electrode by using clean non-woven fabric, then placing the ceramic tube gold electrode on the heating table with the temperature of 120 ℃ for annealing for 1min, taking out the graphite rod after annealing, and then placing the prepared gas-sensitive sensor back into a box;
5) and (3) gas testing: firmly welding the gas sensor obtained in the step 4) on a clean and complete hexagonal base, and then inserting the gas sensor on a test board of a test system. Under the condition of 25 ℃, after a testing system is started to wait for a stable baseline, 6 mu L (50ppm) of ammonia water is measured and injected into an evaporating dish, the ammonia water is heated to be evaporated into a gaseous state and is uniformly mixed by a fan, and after ammonia gas is detected by a sensor, the resistance change of the sensor or the voltage change of a load resistor is read out through the system processing. After the voltage is stabilized, introducing air to stabilize the voltage to a baseline, repeating the step, and sequentially injecting 50ppm, 100ppm, 200ppm, 500ppm, 800ppm and 1000ppm of ammonia gas according to a calculation formula to obtain NH of the gas sensor shown in figure 33For NH concentrations of 50-1000ppm3Exhibit a high response.
XRD (X-ray diffraction) test is carried out on the prepared gas-sensitive sensing material, the characterization result is shown in figure 1, and the result shows that the gas-sensitive sensing material is pure Cs2PbI2(SCN)2Phase (1);
the gas-sensitive sensing material coated on the surface of the gold electrode of the ceramic tube in a rotating way is observed by SEM, SEM pictures under different magnifications are shown in figure 2, and it can be seen from the figure that the perovskite film covers the substrate well, and the film is flat.
Example 2:
1) preparing a perovskite-like precursor solution: 0.4mmol of cesium iodide (CsI) and 0.2mmol of lead thiocyanate (Pb (SCN) were weighed out separately2) And dissolved in a mixed solution of 800mL of DMF and 200mL of DMSO, and then placed on a heating stirring table at 60 ℃ to be heated and stirred for 2 hours to obtain 0.2mmol/mL of Cs2PbI2(SCN)2A solution;
2) pretreating a ceramic tube gold electrode: selecting a ceramic tube gold electrode with a complete gold electrode and a complete Pt wire, and carrying out UVO treatment on the ceramic tube gold electrode for 20 min;
3) solution treatment and preheating of a ceramic tube gold electrode: the Cs obtained in the step 1) is treated2PbI2(SCN)2Transferring the solution and the ceramic tube gold electrode obtained in the step 2) into a nitrogen glove box, and filtering Cs by using a 0.22-micron filter head2PbI2(SCN)2Setting the two heating tables to be 80 ℃ and 120 ℃ respectively for standby, and placing two pieces of 1.5 cm-10 cm soda-lime glass on the two heating tables respectively, wherein the distance between the two pieces of soda-lime glass is about 2 cm;
4) preparation of perovskite-like layer: penetrating a graphite rod with the thickness of 0.5mm through a ceramic tube gold electrode, placing the ceramic tube gold electrode on a heating table with the temperature of 80 ℃, respectively placing two ends of the graphite rod on two pieces of soda-lime glass, preheating for 2min, measuring 3 mu L of solution by using a liquid transfer gun, dripping the solution on the ceramic tube gold electrode, sucking away the redundant solution on the ceramic tube gold electrode by using clean non-woven fabric, then placing the ceramic tube gold electrode on the heating table with the temperature of 120 ℃ for annealing for 1min, taking out the graphite rod after annealing, and then placing the prepared gas-sensitive sensor back into a box;
5) and (3) gas testing: firmly welding the gas sensor obtained in the step 4) on a clean and complete hexagonal base, and then inserting the gas sensor on a test board of a test system. After the test system is started to wait for the base line to be stable, 60 mu L (500ppm) of ammonia water is measured and injected into an evaporation dish, the ammonia water is heated to be evaporated into a gaseous state and is uniformly mixed through a fan, and after ammonia gas is detected by the sensor, the resistance change of the sensor or the voltage change of the load resistance is read through the system processing. After the voltage is stabilized, air is introduced to stabilize the voltage to the baseline, and the step is repeated for 5 times to obtain the gas sensor shown in FIG. 7 with the concentration of500ppm NH3The result of the repeatability test chart shows that the sensitivity change is not obvious after 5 cycles, which indicates that the repeatability of the gas-sensitive sensing material is good;
example 3:
1) preparing a perovskite-like precursor solution: 0.3mmol of cesium iodide (CsI) and 0.3mmol of lead thiocyanate (Pb (SCN) were weighed out separately2) And dissolved in a mixed solution of 600mL of DMF and 200mL of DMSO, followed by stirring and heating on a stirring table at 60 ℃ for 2 hours to obtain Cs2PbI2(SCN)2A solution;
2) pretreating a ceramic tube gold electrode: selecting a ceramic tube gold electrode with a complete gold electrode and a complete Pt wire, and carrying out UVO treatment on the ceramic tube gold electrode for 20 min;
3) solution treatment and preheating of a ceramic tube gold electrode: the Cs obtained in the step 1) is treated2PbI2(SCN)2Transferring the solution and the ceramic tube gold electrode obtained in the step 2) into a nitrogen glove box, and filtering Cs by using a 0.22-micron filter head2PbI2(SCN)2Setting the two heating tables to be 80 ℃ and 120 ℃ respectively for standby, and placing two pieces of 1.5 cm-10 cm soda-lime glass on the two heating tables respectively, wherein the distance between the two pieces of soda-lime glass is about 2 cm;
4) preparation of perovskite-like layer: penetrating a graphite rod with the thickness of 0.5mm through a ceramic tube gold electrode, placing the ceramic tube gold electrode on a heating table with the temperature of 80 ℃, respectively placing two ends of the graphite rod on two pieces of soda-lime glass, preheating for 2min, measuring 3 mu L of solution by using a liquid transfer gun, dripping the solution on the ceramic tube gold electrode, sucking away the redundant solution on the ceramic tube gold electrode by using clean non-woven fabric, then placing the ceramic tube gold electrode on the heating table with the temperature of 120 ℃ for annealing for 1min, taking out the graphite rod after annealing, and then placing the prepared gas-sensitive sensor back into a box;
5) and (3) gas testing: firmly welding the gas sensor obtained in the step 4) on a clean and complete hexagonal base, and then inserting the gas sensor on a test board of a test system. Opening the test system to wait for the baseline to be stable, measuring 6 mu L (50ppm) ammonia water, injecting the ammonia water onto an evaporation dish, heating to evaporate the ammonia water into a gaseous state, uniformly mixing the ammonia water with the vapor by a fan, and detecting by a sensorAfter ammonia gas is detected, the resistance change of the sensor or the voltage change of the load resistance is read through system processing. After the voltage is stabilized, introducing air to stabilize the voltage to a baseline, repeating the steps, sequentially injecting 50ppm, 100ppm, 200ppm, 500ppm and 1000ppm of ammonia gas according to a calculation formula, calculating the sensitivity under each concentration according to the sensitivity Ra/Rg, obtaining a relation graph between the sensitivity and the concentration shown in figure 4, and the result shows that the sensitivity of the gas sensor is increased along with the increase of the ammonia gas concentration, and the linear relation between the sensitivity and the concentration is as follows: 0.00673x +1.07068, where x is concentration, Y is sensitivity, and the correlation coefficient R is2＝0.97。
Example 4:
1) preparing a perovskite-like precursor solution: 0.6mmol of cesium iodide (CsI) and 0.3mmol of lead thiocyanate (Pb (SCN) were weighed out separately2) And dissolved in a mixed solution of 800mL of DMF and 200mL of DMSO, and then placed on a heating stirring table at 65 ℃ to be heated and stirred for 4 hours to obtain 0.3mmol/mL of Cs2PbI2(SCN)2A solution;
2) pretreating a ceramic tube gold electrode: selecting a ceramic tube gold electrode with a complete gold electrode and a complete Pt wire, and carrying out UVO treatment on the ceramic tube gold electrode for 20 min;
3) solution treatment and preheating of a ceramic tube gold electrode: the Cs obtained in the step 1) is treated2PbI2(SCN)2Transferring the solution and the ceramic tube gold electrode obtained in the step 2) into a nitrogen glove box, and filtering Cs by using a 0.22-micron filter head2PbI2(SCN)2Setting the two heating tables to be 80 ℃ and 120 ℃ respectively for standby, and placing two pieces of 1.5 cm-10 cm soda-lime glass on the two heating tables respectively, wherein the distance between the two pieces of soda-lime glass is about 2 cm;
4) preparation of perovskite-like layer: penetrating a graphite rod with the thickness of 0.5mm through a ceramic tube gold electrode, placing the ceramic tube gold electrode on a heating table with the temperature of 80 ℃, respectively placing two ends of the graphite rod on two pieces of soda-lime glass, preheating for 2min, measuring 3 mu L of solution by using a liquid transfer gun, dripping the solution on the ceramic tube gold electrode, sucking away the redundant solution on the ceramic tube gold electrode by using clean non-woven fabric, then placing the ceramic tube gold electrode on the heating table with the temperature of 120 ℃ for annealing for 1min, taking out the graphite rod after annealing, and then placing the prepared gas-sensitive sensor back into a box;
5) and (3) gas testing: firmly welding the gas sensor obtained in the step 4) on a clean and complete hexagonal base, and then inserting the gas sensor on a test board of a test system. After the test system is started to wait for the base line to be stable, 60 mu L (500ppm) of ammonia water is measured and injected into an evaporation dish, the ammonia water is heated to be evaporated into a gaseous state and is uniformly mixed through a fan, and after ammonia gas is detected by the sensor, the resistance change of the sensor or the voltage change of the load resistance is read through the system processing. And after the voltage is stabilized, introducing air to stabilize the gas sensor to a baseline, and obtaining a response-recovery time chart shown in fig. 5 according to the response time from the time when the gas sensor is contacted with the detected gas to the time when the resistivity reaches 90% Rg and the recovery time from the time when the resistivity is reduced to 90% Rg to the time when the baseline is recovered, wherein the results show that the response-recovery time of the gas sensor to ammonia gas is respectively 52s and 61 s.
Example 5:
1) preparing a perovskite-like precursor solution: 0.6mmol of cesium iodide (CsI) and 0.3mmol of lead thiocyanate (Pb (SCN) were weighed out separately2) And dissolved in a mixed solution of 800mL of DMF and 200mL of DMSO, followed by stirring with heating on a stirring table at 60 ℃ for 2 hours to obtain 0.3mmol/mL of Cs2PbI2(SCN)2A solution;
2) pretreating a ceramic tube gold electrode: selecting a ceramic tube gold electrode with a complete gold electrode and a complete Pt wire, and carrying out UVO treatment on the ceramic tube gold electrode for 15 min;
3) solution treatment and preheating of a ceramic tube gold electrode: the Cs obtained in the step 1) is treated2PbI2(SCN)2Transferring the solution and the ceramic tube gold electrode obtained in the step 2) into a nitrogen glove box, and filtering Cs by using a 0.22-micron filter head2PbI2(SCN)2Setting the two heating tables to be 90 ℃ and 110 ℃ respectively for standby, and placing two pieces of 1.5 cm-10 cm soda-lime glass on the two heating tables respectively, wherein the distance between the two pieces of soda-lime glass is about 2 cm;
4) preparation of perovskite-like layer: penetrating a graphite rod with the thickness of 0.5mm through a ceramic tube gold electrode, placing the ceramic tube gold electrode on a heating table with the temperature of 90 ℃, respectively placing two ends of the graphite rod on two pieces of soda-lime glass, preheating for 2min, measuring 3 mu L of solution by using a liquid transfer gun, dripping the solution on the ceramic tube gold electrode, sucking away the redundant solution on the ceramic tube gold electrode by using clean non-woven fabric, then placing the ceramic tube gold electrode on the heating table with the temperature of 110 ℃ for annealing for 1min, taking out the graphite rod after annealing, and then placing the prepared gas-sensitive sensor back into a box;
5) and (3) gas testing: firmly welding the gas sensor obtained in the step 4) on a clean and complete hexagonal base, and then inserting the gas sensor on a test board of a test system. After the test system is started and the baseline is stable, 0.6 mu L (5ppm) of ammonia water is measured and injected into an evaporation dish, the ammonia water is heated to be evaporated into a gaseous state and is uniformly mixed by a fan, and after the ammonia gas is detected by the sensor, the resistance change of the sensor or the voltage change of the load resistance is read out through the system processing. And after the voltage is stabilized, introducing air to stabilize the voltage to a baseline, repeating the step, and sequentially injecting 5ppm, 10ppm and 20ppm of ammonia gas according to a calculation formula to obtain a detection limit diagram of the gas sensor on the ammonia gas as shown in fig. 6, wherein the result shows that the gas sensor still has good response on the ammonia gas with the minimum content of 5 ppm.
Example 6:
1) preparing a perovskite-like precursor solution: 0.6mmol of cesium iodide (CsI) and 0.3mmol of lead thiocyanate (Pb (SCN) were weighed out separately2) And dissolved in a mixed solution of 800mL of DMF and 200mL of DMSO, followed by stirring with heating on a stirring table at 60 ℃ for 2 hours to obtain 0.3mmol/mL of Cs2PbI2(SCN)2A solution;
2) pretreating a ceramic tube gold electrode: selecting a ceramic tube gold electrode with a complete gold electrode and a complete Pt wire, and carrying out UVO treatment on the ceramic tube gold electrode for 20 min;
3) solution treatment and preheating of a ceramic tube gold electrode: the Cs obtained in the step 1) is treated2PbI2(SCN)2Transferring the solution and the ceramic tube gold electrode obtained in the step 2) into a nitrogen glove box, and filtering Cs by using a 0.22-micron filter head2PbI2(SCN)2The solution is ready for use, and two heating tables are respectively arrangedTwo pieces of soda-lime glass of 1.5cm multiplied by 10cm are respectively placed on two heating tables at the temperature of 80 ℃ and 120 ℃, and the distance between the two pieces of soda-lime glass is about 2 cm;
4) preparation of perovskite-like layer: penetrating a graphite rod with the thickness of 0.5mm through a ceramic tube gold electrode, placing the ceramic tube gold electrode on a heating table with the temperature of 80 ℃, respectively placing two ends of the graphite rod on two pieces of soda-lime glass, preheating for 5min, measuring 4 mu L of solution by using a liquid transfer gun, dripping the solution on the ceramic tube gold electrode, sucking away the redundant solution on the ceramic tube gold electrode by using clean non-woven fabric, then placing the ceramic tube gold electrode on the heating table with the temperature of 120 ℃ for annealing for 2min, taking out the graphite rod after annealing, and then placing the prepared gas-sensitive sensor back into a box;
5) and (3) gas testing: firmly welding the gas sensor obtained in the step 4) on a clean and complete hexagonal base, and then inserting the gas sensor on a test board of a test system. After the test system is started to wait for the base line to be stable, 60 mu L (500ppm) of ammonia water is measured and injected into an evaporation dish, the ammonia water is heated to be evaporated into a gaseous state and is uniformly mixed through a fan, and after ammonia gas is detected by the sensor, the resistance change of the sensor or the voltage change of the load resistance is read through the system processing. After the voltage is stabilized, introducing air to stabilize the voltage to a baseline, repeating the step, and sequentially injecting 500ppm of ammonia, acetone, toluene, methanol and ethanol according to a calculation formula to obtain a selectivity test chart of the gas sensor on different gases as shown in fig. 8, wherein the result shows that the gas sensor can test the ammonia NH (NH) with the concentration of 500ppm3Acetone CH3COCH3Toluene C7H8Methanol CH3OH, ethanol C2H5The sensitivity of OH is 5.152, 1.077, 1.09, 1.068 and 1.04 respectively, and the sensitivity shows obvious high selectivity to ammonia gas.
Claims (9)
1. The perovskite-like gas-sensitive sensing material is characterized in that the gas-sensitive sensing material is Cs2PbI2(SCN)2(ii) a The working temperature of the gas-sensitive sensing material is 20-30 ℃; the gas-sensitive sensing material is suitable for ammonia NH3Acetone CH3COCH3Toluene C7H8Methanol CH3OH or ethanolC2H5OH。
2. A gas sensor prepared by using the perovskite-like gas-sensitive sensing material as claimed in claim 1, wherein the gas sensor comprises the gas-sensitive sensing material and an electrode for the gas sensor, and the surface of the electrode for the gas sensor is wrapped by the gas-sensitive sensing material.
3. The preparation method of the perovskite-like gas sensor as claimed in claim 2, which is characterized by comprising the following steps:
1) preparation of Cs2PbI2(SCN)2A solution; cs2PbI2(SCN)2The concentration of the solution is 0.1-0.9 mmol/mL;
2) selecting a ceramic tube gold electrode with good wiring, and treating by adopting an ultraviolet ozone cleaning machine;
3) preheating the ceramic tube gold electrode obtained in the step 2);
4) dripping the solution obtained in the step 1) on the ceramic tube gold electrode obtained in the step 3) to enable the solution to completely wrap the ceramic tube gold electrode, and then carrying out heating annealing to prepare the inorganic material perovskite-like gas sensor.
4. The method as claimed in claim 3, wherein the amount of the dropping solution in the step 4) is 1-5 μ L, the annealing temperature is 100-130 ℃, and the annealing time is 1-3 min.
5. The method according to claim 3, wherein Cs is used in the step 1)2PbI2(SCN)2The specific preparation method of the solution comprises the following steps: dissolving cesium iodide and lead thiocyanate solids in an organic solvent, and heating, stirring and dissolving;
the mass ratio of cesium iodide to lead thiocyanate is 1:1-3: 1; the heating and stirring temperature is 60-70 ℃, and the heating and stirring time is 2-12 h;
the organic solvent is a mixed solution of N, N-dimethylformamide and dimethyl sulfoxide, and the volume ratio of the N, N-dimethylformamide to the dimethyl sulfoxide is 4:1-0: 1.
6. The method according to claim 3, wherein the treatment time in the step 2) is 10 to 20 min.
7. The preparation method according to claim 3, wherein the gold electrode of the ceramic tube in the step 2) is a thin-wall ceramic tube, and the gold electrode and the platinum-iridium alloy wire are respectively arranged at two ends of the tube body.
8. The method according to claim 3, wherein the preheating temperature in the step 3) is 80 to 100 ℃ and the preheating time is 2 to 10 min.
9. The method of claim 3, wherein step 3) and step 4) are performed in a nitrogen glove box.
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