CN112320859A - NiO-SnO2Preparation method and application of flower-shaped structure composite material - Google Patents
NiO-SnO2Preparation method and application of flower-shaped structure composite material Download PDFInfo
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Abstract
NiO-SnO2A method for preparing a composite material with a flower-shaped structure and application thereof relate to a method for preparing a gas sensitive material and application thereof, wherein a low-temperature one-step hydrothermal method is adopted in the synthetic method, stannous chloride and nickel nitrate which are cheap and easy to obtain are used as raw materials, sodium citrate is used as an auxiliary agent, and NiO-SnO is prepared by a one-step hydrothermal synthesis technology under mild conditions2Flower-like structural composites. And the composite material is applied to the field of gas sensors. The whole production process has simple process, strong operability, no toxicity and no harm, and is suitable for large-scale industrial production. The composite material prepared by the invention not only has a unique three-dimensional flower-shaped structure, but also constructs a multi-level pore channel, so that gas to be detected can be diffused in the material more quickly, and simultaneously, a p-n heterojunction is introduced, so that a material pair is formedThe ethanol gas has high sensitivity and selectivity, quick response and recovery characteristics and good stability, and has wide prospect in the aspect of manufacturing of gas sensors.
Description
Technical Field
The invention relates to a preparation method and application of a gas-sensitive material, in particular to a gas-sensitive materialNiO-SnO2A preparation method and application of a flower-shaped structure composite material.
Background
The ethanol belongs to a popular chemical product with wide application, simple production process and sufficient raw material supply, and is widely applied to national defense industry, medical treatment and health, organic synthesis, food industry, industrial and agricultural production. However, ethanol vapor is toxic, flammable, and explosive. In industrial production and daily life, if leakage happens carelessly, serious accidents such as explosion, fire and the like can happen at any time. In addition, ethanol can inhibit the central nervous system of a human body, which leads to neuropathy and even death, and meanwhile, traffic accidents caused by drunk driving sometimes occur. Therefore, in order to ensure the safety of production and life of people, effective detection of ethanol gas is necessary. Compared with the traditional gas detection means (chromatography, molecular imprinting, colorimetry and the like), the gas sensor can monitor the existence of various explosive, combustible and toxic gases on line in real time, so that people can effectively perceive the safety of the surrounding environment in time, serious accidents such as fire, explosion and poisoning are effectively prevented, and further the life safety damage and property loss of people are avoided; more importantly, the device can detect whether toxic gas leakage exists in a large-scale factory or not, thereby ensuring the production safety and healthy life of people. On the other hand, the drunk driving detection method effectively avoids traffic accidents and ensures the happiness and the health of people. At present, although the development of gas sensors is mature, the performance of the gas sensors still needs to be further improved. Therefore, the high-performance ethanol gas sensor is developed, and the ethanol gas is effectively monitored in real time, so that the harm of ethanol to production and life is reduced, and the method has very important significance.
SnO2The N-type semiconductor material is an important n-type semiconductor material, is widely applied to detection of various flammable and explosive gases, toxic and harmful gases, environmental pollution gases and other fields, and has a wide prospect in the field of semiconductor gas sensors. The results of the study show that the compounds are expressed as SnO2The gas sensor prepared from the gas sensitive material has the advantages of wide detection range, good chemical stability and sensitivityThe semiconductor sensitive material has the advantage of high degree, and is a semiconductor sensitive material which is researched more and has a wider application range at present. However, currently SnO2The indexes of sensitivity, detection temperature and the like of the base gas sensor still need to be further improved. SnO2The sensitive mechanism of the gas sensitive material is that the gas sensitive material is contacted with different types of gases to cause resistance change to effectively detect related gases, and the large surface area can enable a large number of gas molecules to be rapidly adsorbed on the surface of the material, so that the detection characteristic is effectively improved. With the rapid development of nanotechnology, nano-structured materials such as nano-sheets, nano-particles, nano-rods and the like are synthesized into three-dimensional micro-nano structured materials (flower-shaped, spherical and sea urchin-shaped) through various synthesis methods, so that the materials have higher specific surface area and hierarchical pores, can adsorb more target gas molecules, and further show excellent sensitivity. But the gas-sensitive performance of the material can not be greatly improved by singly optimizing the structure of the sensitive material. In order to develop a gas sensor with higher sensitivity and high selectivity, the gas-sensitive material is modified by adding SnO2The second metal oxide is modified on the surface of the nano material to improve the gas-sensitive performance of the gas sensor, and the method is an effective method for improving the performance of the semiconductor gas sensor. NiO is used as a p-type semiconductor and has the advantages of high catalytic performance, high stability and the like. The invention improves SnO by adding NiO and forming p-n heterojunction2Gas-sensitive properties of the sensitive material.
Disclosure of Invention
The invention aims to provide NiO-SnO2The invention discloses a preparation method and application of a flower-shaped structure composite material2The flower-shaped structure composite material is applied to the detection of ethanol gas.
The purpose of the invention is realized by the following technical scheme:
NiO-SnO2A method for preparing a composite material with a flower-like structure, the method comprising the following preparation steps:
the method comprises the following steps: dissolving stannous chloride, nickel nitrate and sodium citrate in a mixed solution prepared from 40 mL of ethanol and 40 mL of distilled water, magnetically stirring for 30 minutes at room temperature until the stannous chloride, the nickel nitrate and the sodium citrate are completely dissolved, and preparing a hydro-thermal synthesis precursor reaction solution;
step two: transferring the precursor reaction solution prepared in the step one into a high-pressure reaction kettle with a polytetrafluoroethylene stainless steel lining, wherein the filling degree is 80%, and sealing; preserving the heat for 12 hours at the temperature of 180 ℃, and then cooling to room temperature along with the furnace to obtain a reaction product;
step three: centrifuging the product obtained in the step two to obtain a reaction product, repeatedly washing the reaction product by using distilled water and absolute ethyl alcohol, and then drying the reaction product at the temperature of 60 ℃ for 24 hours;
step four: putting the product dried in the third step into a muffle furnace, and calcining for 4 hours at 500 ℃ to obtain NiO-SnO2Flower-like structural composites.
NiO-SnO2Application of composite material with flower-like structure by using NiO-SnO2The flower-shaped structure composite material is used as a gas sensitive material, and the application steps for manufacturing the gas sensor are as follows:
the method comprises the following steps: NiO-SnO2Adding ethanol into the composite material with the flower-shaped structure to prepare slurry, and coating the slurry on an alumina ceramic substrate with interdigital gold electrodes and four platinum wires;
step two: drying the material under the irradiation of an infrared lamp;
step three: respectively welding four conductive wires of the ceramic substrate on a four-pin base to prepare a gas sensor element;
step four: aging the prepared gas sensor element on an aging table for 2 days;
step five: and a WS-30A gas-sensitive tester is adopted to test the gas sensitivity characteristic of the sensor. The test temperature is 50-350 ℃.
The invention has the advantages and beneficial effects that:
the starting raw materials for preparing the target product are stannous chloride and nickel nitrate which are widely used popular chemical raw materials, and Ni with stable structure appearance, uniform size and good crystallinity is obtained by low-temperature hydrothermal reaction and treatment processes such as centrifugation, washing, drying, calcination and the likeO-SnO2Flower-like structural composites. The prepared NiO-SnO2The flower-shaped structure composite material is assembled by nanosheets with similar shapes and sizes, and the diameter of the flower-shaped structure composite material is 1-2 mu m. The thickness of the nano-sheets is about 10-20 nm, and the distance between every two adjacent nano-sheets is large, so that the adsorption and desorption of target gas are facilitated. NiO-SnO2The gas sensor prepared from the composite material with the flower-shaped structure has higher sensitivity to ethanol, good response-recovery characteristic and selectivity due to the unique spatial structure.
(1) The invention takes stannous chloride and nickel nitrate as raw materials to synthesize NiO-SnO assembled by nano sheets under the low-temperature hydrothermal condition2Flower-like structural composites. The method has the advantages of low cost, good controllability, high purity of the prepared material, good crystallization and good dispersibility, and is suitable for large-scale industrial production.
(2) NiO-SnO prepared by the invention2The flower-shaped structure composite material has a unique spatial structure, so that the specific surface area of the material is increased, and a developed porous channel is constructed, so that the material has better permeability, the sensitivity of the sensitive material to ethanol gas is greatly improved, the capability, selectivity and stability of repeated response and recovery are improved, and the flower-shaped structure composite material has a wide application prospect in the aspect of detecting the ethanol gas.
(3) NiO-SnO prepared by the invention2The ethanol-based gas sensor has simple manufacturing process and low cost, and is suitable for large-scale industrial mass production.
Drawings
FIG. 1 is an X-ray diffraction pattern of a product of the present invention;
FIG. 2(a) is a scanning electron micrograph of a product prepared in example 1;
FIG. 2(b) scanning electron micrograph of product prepared in example 2;
FIG. 2(c) is a scanning electron micrograph of a product prepared in example 3;
FIG. 2(d) is a scanning electron micrograph of the product prepared in example 4;
FIG. 2(e) is a scanning electron micrograph of a product prepared in example 5;
FIG. 2(f) is a scanning electron micrograph of a product prepared in example 6;
FIG. 3(a) is a photograph of a gas sensor element;
FIG. 3(b) is a graph of sensitivity of a gas sensor to 10 ppm ethanol gas as a function of operating temperature;
FIG. 3(c) shows example 4 (5% NiO-SnO)2) A dynamic response curve chart of the gas sensor to ethanol gas with different concentrations at 150 ℃;
FIG. 3(d) is a graph of example 4 (5% NiO-SnO)2) A graph of the change of the concentration of the ethanol gas with the sensitivity of the gas sensor at 150 ℃;
FIG. 3(e) is a graph showing example 4 (5% NiO-SnO)2) A selectivity profile of the gas sensor at 150 ℃ for 10 ppm of different reducing gases;
FIG. 3(f) is a graph of example 4 (5% NiO-SnO)2) Long-term stability plot of gas sensor at 150 ℃ against 10 ppm ethanol gas.
Detailed Description
The present invention will be described in detail with reference to the embodiments shown in the drawings.
Example 1
(1) Preparation of SnO2Flower-like structural material
The method comprises the following steps: 2.3 g of stannous chloride and 5.9 g of sodium citrate are weighed by balance, dissolved in a mixed solution prepared from 40 mL of ethanol and 40 mL of distilled water, and magnetically stirred for 30 minutes at room temperature until the stannous chloride and the distilled water are completely dissolved to prepare a hydrothermal synthesis precursor solution.
Step two: transferring the precursor reaction solution prepared in the step one into a high-pressure reaction kettle with a polytetrafluoroethylene stainless steel lining, wherein the filling degree is 80%, and sealing.
Step three: and (5) placing the reaction kettle in the second step into an oven, preserving the heat for 12 hours at the temperature of 180 ℃, and then cooling.
Step four: and (4) centrifugally separating the reactant solution prepared in the step three to obtain a precipitate, and repeatedly washing the precipitate by using distilled water and absolute ethyl alcohol.
Step five: and (4) putting the product obtained in the step four into a drying box with a constant temperature, drying for 24 hours at 60 ℃, and cooling after drying.
Step six: putting the product dried in the fifth step into a clean crucible, putting the crucible into a muffle furnace, and calcining the crucible for 4 hours at 500 ℃ to obtain SnO2Powder, which is stored in a desiccator for analytical testing.
（2）SnO2Structural characterization of flower-like structural materials
The crystal structure of the product was characterized using an XRD powder diffractometer (XRD, PANALYTICAL X' Pert Pro). Fig. 1 is an X-ray diffraction (XRD) pattern of a sample. It can be seen from the figure that the diffraction characteristic peaks are all sharp, and no other impurity peaks appear, indicating that the prepared sample has high purity and crystallinity. The diffraction characteristic peak completely accords with NO.41-1445 in the standard PDF card, which indicates that the sample is monoclinic SnO2。
The morphology of the product was characterized by scanning electron microscopy (FESEM, ZEISS Ultra Plus). As shown in FIG. 2(a), the product is flower-shaped, and is formed by self-assembling a plurality of nano sheets with the thickness of about 10-20 nm, the diameter is 1-2 mu m, the dispersibility is good, and a large number of pores are formed on the surface of the powder.
Example 2
(1) Preparation of 1% NiO-SnO2Flower-like structure composite material
The method comprises the following steps: 2.3 g of stannous chloride, 0.02 g of nickel nitrate and 5.9 g of sodium citrate are dissolved in a mixed solution prepared from 40 mL of ethanol and 40 mL of distilled water, and the mixture is magnetically stirred for 30 minutes at room temperature until the mixture is completely dissolved to prepare a hydrothermal synthesis precursor reaction solution.
The second, third, fourth, fifth and sixth steps are the same as in example 1.
（2）1%NiO-SnO2Structural characterization of flower-like structural composites
The crystal structure of the product was characterized using an XRD powder diffractometer (XRD, PANALYTICAL X' Pert Pro). It can be seen from FIG. 1 that the sample has a monoclinic phase-removed SnO2No NiO diffraction peaks appeared, probably because the NiO content was relatively low and the NiO particle size was relatively small. Diffraction characteristic peaks allIt is very sharp and no other peaks appear, indicating that the purity and crystallinity of the prepared sample are high. And characterizing the morphology of the product by adopting a scanning electron microscope. As shown in FIG. 2(b), the morphology thereof appeared flower-like, similar to that of example 1 (pure SnO)2) The appearance is consistent and has no obvious change.
Example 3
(1) Preparation of 3% NiO-SnO2Flower-like structure composite material
The method comprises the following steps: 2.3 g of stannous chloride, 0.07 g of nickel nitrate and 5.9 g of sodium citrate are dissolved in a mixed solution prepared from 40 mL of ethanol and 40 mL of distilled water, and the mixture is magnetically stirred for 30 minutes at room temperature until the mixture is completely dissolved to prepare a hydrothermal synthesis precursor reaction solution.
The second, third, fourth, fifth and sixth steps are the same as in example 1.
（2）3%NiO-SnO2Structural characterization of flower-like structural composites
The crystal structure of the product was characterized using an XRD powder diffractometer (XRD, PANALYTICAL X' Pert Pro). It can be seen from FIG. 1 that the sample has a monoclinic phase-removed SnO2No NiO diffraction peak appeared, possibly because the NiO content was relatively low, the particle size was relatively small. The diffraction characteristic peaks are sharp, and no other impurity peaks appear, which indicates that the prepared sample has high purity and crystallinity. And characterizing the morphology of the product by adopting a scanning electron microscope. As shown in FIG. 2(c), the morphology thereof appeared flower-like, similar to that of example 1 (pure SnO)2) The appearance is consistent and has no obvious change.
Example 4
(1) Preparation of 5% NiO-SnO2Flower-like structure composite material:
the method comprises the following steps: 2.3 g of stannous chloride, 0.11 g of nickel nitrate and 5.9 g of urea are dissolved in a mixed solution prepared from 40 mL of ethanol and 40 mL of distilled water, and the mixture is magnetically stirred for 30 minutes at room temperature until the mixture is completely dissolved to prepare a hydrothermal synthesis precursor reaction solution.
The second, third, fourth, fifth and sixth steps are the same as in example 1.
（2）5%NiO-SnO2Structural characterization of flower-like structural composites
The crystal structure of the product was characterized using an XRD powder diffractometer (XRD, PANALYTICAL X' Pert Pro). FIG. 1 shows that the sample has a monoclinic phase-removed SnO2No NiO diffraction peaks appeared, probably due to the lower NiO content and smaller particle size. The diffraction characteristic peaks are sharp, and no other impurity peaks appear, which indicates that the prepared sample has high purity and crystallinity. And characterizing the morphology of the product by adopting a scanning electron microscope. As shown in FIG. 2(d), the morphology thereof appeared flower-like, similar to that of example 1 (pure SnO)2) The shapes are consistent, no obvious change exists, and the surfaces of the ball flowers become rough along with the increase of the content of the NiO nano particles.
Example 5
(1) Preparation of 7% NiO-SnO2Flower-like structure composite material
The method comprises the following steps: 2.3 g of stannous chloride, 0.16 g of nickel nitrate and 5.9 g of sodium citrate are dissolved in a mixed solution prepared from 40 mL of ethanol and 40 mL of distilled water, and the mixture is magnetically stirred for 30 minutes at room temperature until the mixture is completely dissolved to prepare a hydrothermal synthesis precursor reaction solution.
The second, third, fourth, fifth and sixth steps are the same as in example 1.
（2）7%NiO-SnO2Structural characterization of flower-like structural composites
The crystal structure of the product was characterized using an XRD powder diffractometer (XRD, PANALYTICAL X' Pert Pro). FIG. 1 shows that the sample has a monoclinic phase-removed SnO2In addition to the peak(s), 1 distinct NiO diffraction peak appears, corresponding to the standard card number (JPCDS card number 73-1523). And no other impurity diffraction peaks are found in characteristic peaks of all products, which shows that the products are mainly formed by SnO2And NiO, and has high purity and crystallinity. And characterizing the morphology of the product by adopting a scanning electron microscope. As shown in FIG. 2(e), the morphology thereof appeared flower-like, similar to that of example 1 (pure SnO)2) The shapes are consistent, no obvious change exists, and the surfaces of the ball flowers become rougher along with the increase of the content of the NiO nano particles.
Example 6
(1) Preparation of 10% NiO-SnO2Flower-like structure composite material
The method comprises the following steps: 2.3 g of stannous chloride, 0.23 g of nickel nitrate and 5.9 g of sodium citrate are dissolved in a mixed solution prepared from 40 mL of ethanol and 40 mL of distilled water, and the mixed solution is magnetically stirred for 30 minutes at normal temperature until the mixed solution is completely dissolved to prepare a hydrothermal synthesis precursor reaction solution.
The second, third, fourth, fifth and sixth steps are the same as in example 1.
（2）10%NiO-SnO2Structural characterization of flower-like structural composites
The crystal structure of the product was characterized using an XRD powder diffractometer (XRD, PANALYTICAL X' Pert Pro). FIG. 1 shows that the sample has a monoclinic phase-removed SnO2In addition to the peak(s), 1 distinct NiO diffraction peak appears, corresponding to the standard card number (JPCDS card number 73-1523). And no other impurity diffraction peaks are found in characteristic peaks of all products, which shows that the products are mainly formed by SnO2And NiO, and has high purity and crystallinity. And characterizing the morphology of the product by adopting a scanning electron microscope. As shown in FIG. 2(f), the morphology thereof appeared flower-like, similar to that of example 1 (pure SnO)2) The shapes are consistent, no obvious change exists, and the surfaces of the ball flowers become rougher along with the increase of the content of the NiO nano particles.
NiO-SnO prepared in the examples2The flower-shaped nano-structure composite material is prepared into a gas sensor, and the gas sensor is used for carrying out related gas-sensitive performance test on ethanol gas:
weighing a certain amount of NiO-SnO2Ethanol is added into the flower-shaped nano-structure composite material to prepare slurry, and the slurry is coated on an alumina ceramic substrate with interdigital gold electrodes and four platinum wires. After the material is dried under the irradiation of the infrared lamp, the four conductive wires of the ceramic substrate are respectively welded on the four-leg base, so as to prepare the gas sensor element, as shown in fig. 3 (a). And a WS-30A gas-sensitive tester is adopted to test the gas sensitivity characteristic of the sensor.
The sensitivity of the gas sensor to 10 ppm ethanol gas as a function of operating temperature is shown in FIG. 3 (b). As can be seen from the figure, in the temperature interval of 50 ℃ to 350 ℃, the sensitivity of all gas sensors first increases with increasing operating temperature, reaches a maximum value, and then gradually decreases.Example 1 (pure SnO2) And example 2 (1% NiO-SnO)2) The optimal working temperature of the sensor is 200 ℃, and the maximum sensitivity is 5.6 and 6.7 respectively; example 3 (3% NiO-SnO)2) Example 4 (5% NiO-SnO)2) Example 5 (7% NiO-SnO)2) Example 6 (10% NiO-SnO)2) The optimum operating temperature of the sensor is 150 ℃ and the maximum response values are 7.9, 9.2, 8.5 and 7.3, respectively. This is indicated in SnO2NiO properly modified on the surface of the gas sensitive material can not only reduce the working temperature, but also improve the sensitivity to ethanol. The sensor of example 4 having the highest sensitivity was selected as the best sensor and tested for its sensitivity.
For further understanding of example 4 (5% NiO-SnO)2) The sensitivity of the sensor, measured the dynamic response-recovery characteristics at 150 ℃ for different ethanol concentrations (1-200 ppm). As shown in fig. 3 (c). As is apparent from the graph, the resistance sharply decreases when the sensor is exposed to the ethanol gas, and then returns to the initial state after the ethanol gas is removed, and repeated exposure to ethanol gas of different concentrations has no significant stagnation, indicating stable and repeatable sensitivity characteristics of the sensor material. FIG. 3(d) is a graph of example 4 (5% NiO-SnO)2) The sensitivity curve of the gas sensor to the ethanol gas concentration along with the change of the sensitivity shows that the sensitivity of the sensor increases along with the increase of the ethanol concentration at the optimal temperature, the sensitivity rising trend of the sensor increases along with the increase of the ethanol concentration at 1-200ppm, and the sensitivity rising trend of the sensor gradually decreases after the concentration is higher than 50 ppm, which shows that the sensor is gradually saturated, probably due to SnO2A large number of ethanol molecules are adsorbed on the surface of the material, and the area of the surface capable of adsorbing the ethanol molecules is greatly reduced, so that the surface reaction is reduced, and the sensitivity rising trend is reduced. The change curve of the sensitivity of the sensor along with the concentration proves that the sensor prepared in the embodiment 4 can detect the ethanol gas in a wider range (1-200 ppm), and particularly the detection characteristic of the sensor under low concentration can realize accurate detection of the ethanol gas in the fields of environment, drunk driving detection and the like. FIG. 3(e) is a graph showing example 4 (5% NiO-SnO)2) Medium gas sensorSelectivity profile at 150 ℃ for different reducing gases of 10 ppm. As can be seen from the figure, the sensor in example 4 has higher sensitivity to ethanol than other gases, among the 6 gases tested, than benzene, toluene, acetone, methanol, propanol, etc., which indicates that the sensor has good selectivity to ethanol. FIG. 3(f) is a graph showing the results of the sensitivity test of the sensor in example 4 at 150 ℃ to 10 ppm of ethanol gas for 60 consecutive days. As can be seen from the figure, no significant degradation in sensitivity was observed during the test, indicating that example 4 has good long-term stability.
Claims (2)
1. NiO-SnO2The preparation method of the flower-shaped structure composite material is characterized by comprising the following preparation steps of:
the method comprises the following steps: dissolving stannous chloride, nickel nitrate and sodium citrate in a mixed solution prepared from 40 mL of ethanol and 40 mL of distilled water, magnetically stirring for 30 minutes at room temperature until the stannous chloride, the nickel nitrate and the sodium citrate are completely dissolved, and preparing a hydro-thermal synthesis precursor reaction solution;
step two: transferring the precursor reaction solution prepared in the step one into a high-pressure reaction kettle with a polytetrafluoroethylene stainless steel lining, wherein the filling degree is 80%, and sealing; preserving the heat for 12 hours at the temperature of 180 ℃, and then cooling to room temperature along with the furnace to obtain a reaction product;
step three: centrifuging the product obtained in the step two to obtain a reaction product, repeatedly washing the reaction product by using distilled water and absolute ethyl alcohol, and then drying the reaction product at the temperature of 60 ℃ for 24 hours;
step four: putting the product dried in the third step into a muffle furnace, and calcining for 4 hours at 500 ℃ to obtain NiO-SnO2Flower-like structural composites.
2. NiO-SnO2The application of the flower-shaped structure composite material is characterized in that NiO-SnO is utilized2The flower-shaped structure composite material is used as a gas sensitive material, and the application steps for manufacturing the gas sensor are as follows:
the method comprises the following steps: NiO-SnO2Adding ethanol into the composite material with the flower-shaped structure to prepare slurry, and coating the slurry on the interdigital gold electrodeAnd four platinum wires on the alumina ceramic substrate;
step two: drying the material under the irradiation of an infrared lamp;
step three: respectively welding four conductive wires of the ceramic substrate on a four-pin base to prepare a gas sensor element;
step four: aging the prepared gas sensor element on an aging table for 2 days;
step five: a WS-30A gas-sensitive tester is adopted to test the gas sensitivity characteristic of the sensor; the test temperature is 50-350 ℃.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113030194A (en) * | 2021-02-03 | 2021-06-25 | 中国科学院合肥物质科学研究院 | Gas sensor array, three alcohol types and identification method of concentration of three alcohol types |
| CN113155912A (en) * | 2021-04-16 | 2021-07-23 | 沈阳化工大学 | Preparation method and application of CuO-ZnO flower-shaped structure composite sensitive material |
| CN113223866A (en) * | 2021-04-15 | 2021-08-06 | 山东科技大学 | SnO (stannic oxide)2Preparation and application of @ PPy/carbon cloth composite electrode material |
| CN113618272A (en) * | 2021-09-23 | 2021-11-09 | 重庆大学 | Flower-shaped core-shell structure composite energetic material and preparation method thereof |
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