CN111458381A - Colorimetric humidity-sensitive material and preparation method and application thereof - Google Patents
Colorimetric humidity-sensitive material and preparation method and application thereof Download PDFInfo
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- 239000000463 material Substances 0.000 title claims abstract description 77
- 238000002360 preparation method Methods 0.000 title abstract description 8
- 239000004642 Polyimide Substances 0.000 claims abstract description 32
- 229920001721 polyimide Polymers 0.000 claims abstract description 32
- 238000000034 method Methods 0.000 claims abstract description 22
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 33
- 239000011521 glass Substances 0.000 claims description 21
- 239000000243 solution Substances 0.000 claims description 21
- 239000000376 reactant Substances 0.000 claims description 18
- 239000000758 substrate Substances 0.000 claims description 18
- 239000000843 powder Substances 0.000 claims description 15
- 239000002904 solvent Substances 0.000 claims description 11
- 238000000227 grinding Methods 0.000 claims description 8
- 239000011259 mixed solution Substances 0.000 claims description 8
- 238000002156 mixing Methods 0.000 claims description 8
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 claims description 6
- 239000002243 precursor Substances 0.000 claims description 6
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 4
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 3
- 229930188620 butyrolactone Natural products 0.000 claims description 3
- 238000001704 evaporation Methods 0.000 claims description 3
- 238000003701 mechanical milling Methods 0.000 claims 1
- 230000004044 response Effects 0.000 abstract description 8
- 230000035945 sensitivity Effects 0.000 abstract description 8
- -1 nickel halide Chemical class 0.000 abstract description 6
- 229910052759 nickel Inorganic materials 0.000 abstract description 5
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 abstract description 5
- 239000003086 colorant Substances 0.000 abstract description 3
- 239000003446 ligand Substances 0.000 abstract description 3
- 239000013110 organic ligand Substances 0.000 abstract description 3
- 238000012271 agricultural production Methods 0.000 abstract description 2
- 238000004140 cleaning Methods 0.000 description 12
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 10
- 238000004528 spin coating Methods 0.000 description 10
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 8
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 8
- 239000007795 chemical reaction product Substances 0.000 description 7
- 239000006185 dispersion Substances 0.000 description 7
- 238000000137 annealing Methods 0.000 description 6
- BFSQJYRFLQUZKX-UHFFFAOYSA-L nickel(ii) iodide Chemical compound I[Ni]I BFSQJYRFLQUZKX-UHFFFAOYSA-L 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- 239000007788 liquid Substances 0.000 description 5
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- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 4
- 230000008901 benefit Effects 0.000 description 4
- 239000008367 deionised water Substances 0.000 description 4
- 229910021641 deionized water Inorganic materials 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 238000011084 recovery Methods 0.000 description 4
- 238000000861 blow drying Methods 0.000 description 3
- 230000007613 environmental effect Effects 0.000 description 3
- 239000011812 mixed powder Substances 0.000 description 3
- 239000002861 polymer material Substances 0.000 description 3
- 238000007650 screen-printing Methods 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 229910001385 heavy metal Inorganic materials 0.000 description 2
- 229910017053 inorganic salt Inorganic materials 0.000 description 2
- 238000012544 monitoring process Methods 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
- 239000004038 photonic crystal Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 230000004580 weight loss Effects 0.000 description 2
- 238000003723 Smelting Methods 0.000 description 1
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Classifications
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
- G01N27/02—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating impedance
- G01N27/04—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating impedance by investigating resistance
- G01N27/12—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating impedance by investigating resistance of a solid body in dependence upon absorption of a fluid; of a solid body in dependence upon reaction with a fluid, for detecting components in the fluid
- G01N27/121—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating impedance by investigating resistance of a solid body in dependence upon absorption of a fluid; of a solid body in dependence upon reaction with a fluid, for detecting components in the fluid for determining moisture content, e.g. humidity, of the fluid
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/75—Systems in which material is subjected to a chemical reaction, the progress or the result of the reaction being investigated
- G01N21/77—Systems in which material is subjected to a chemical reaction, the progress or the result of the reaction being investigated by observing the effect on a chemical indicator
- G01N21/78—Systems in which material is subjected to a chemical reaction, the progress or the result of the reaction being investigated by observing the effect on a chemical indicator producing a change of colour
- G01N21/81—Indicating humidity
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
- G01N27/02—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating impedance
- G01N27/04—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating impedance by investigating resistance
- G01N27/12—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating impedance by investigating resistance of a solid body in dependence upon absorption of a fluid; of a solid body in dependence upon reaction with a fluid, for detecting components in the fluid
- G01N27/125—Composition of the body, e.g. the composition of its sensitive layer
- G01N27/126—Composition of the body, e.g. the composition of its sensitive layer comprising organic polymers
Abstract
The invention discloses a colorimetric humidity-sensitive material and a preparation method and application thereof. Polyimide (PI) is used as an organic ligand, nickel halide is used as an inorganic ligand, and PI-NiX with excellent humidity response performance is prepared2A colorimetric moisture-sensitive material. The colorimetric humidity sensor prepared by the method has obvious difference in characteristic colors in different humidity atmospheres, has very short response time and extremely high sensitivity, and greatly improves the high and low temperature stability of the sensor. The colorimetric humidity-sensitive material disclosed by the invention well keeps the stability of polyimide, has excellent high and low temperature stability, and can still normally work at the temperature range of as low as-80 ℃ and as high as 300 ℃. Therefore, the method has wide application prospect in the special industrial fields of agricultural production, information sensing, nuclear industry, military industry and the like.
Description
Technical Field
The invention relates to the technical field of humidity sensors, in particular to a high-stability and high-sensitivity colorimetric humidity sensitive material and a preparation method and application thereof.
Background
Humidity is closely related to life of people, and humidity sensors are widely applied to daily life, and for example, the humidity sensors are required to be used in production and manufacturing environments of electronic elements, packaging detection, food preservation and the like. It is worth noting that in some special fields such as military industry, nuclear power stations, high-temperature smelting plants and the like, wide requirements for humidity monitoring are also provided.
Most humidity sensors researched by people at present measure relative humidity through changes of electrical parameters such as resistance and capacitance, and can monitor humidity only through matched auxiliary circuits and equipment, so that the complexity and instability of the humidity sensor are increased, and the humidity sensor is not beneficial to application in special fields.
In recent years, colorimetric humidity sensors have been developed to greatly simplify the humidity detection process. People can conveniently and quickly know the relative humidity value by monitoring the electric signal and the surface color of the device simultaneously. Colorimetric humidity-sensitive materials can be roughly classified into four types, namely photonic crystal materials, polymers, inorganic salts and organic-inorganic hybrid materials according to material properties. The photonic crystal material has high cost, the preparation process is not environment-friendly, the polymer material has poor stability and low sensitivity, and the inorganic salt material is less concerned because of easy deliquescence and failure.
Organic and inorganic hybrid colorimetric humidity-sensitive materials are paid more and more attention because of low cost and hopeful of having the advantages of inorganic salts and polymer materials. However, the current organic-inorganic hybrid materials have poor humidity sensitivity, and the problems of poor stability of polymer materials, easy deliquescence of inorganic salt materials, heavy metal content and the like exist, so that the further application of the hybrid materials is limited.
Therefore, how to obtain a colorimetric humidity-sensitive material with high stability, high sensitivity and low cost, and a humidity sensor with good performance is a problem that needs to be solved by those skilled in the art.
Disclosure of Invention
In view of the above, the invention provides a colorimetric humidity-sensitive material and a preparation method and application thereof, and the colorimetric humidity-sensitive material prepared by adopting a molecular design thought and taking polyimide with excellent engineering performance as an organic ligand of an organic-inorganic hybrid material and nickel halide as an inorganic ligand has the advantages of high stability of polyimide and high sensitivity of nickel halide, excellent colorimetric humidity-sensitive property, excellent stability and environmental friendliness. The prepared colorimetric humidity sensitive material is used for manufacturing a humidity sensor, so that the humidity sensor with stable high and low temperature performance and high sensitivity is obtained.
In order to achieve the purpose, the invention adopts the following technical scheme:
a colorimetric moisture-sensitive material comprises polyimide and NiX2(ii) a Wherein X in the formula is selected from I, Cl and Br.
A method for preparing a colorimetric humidity-sensitive material comprises the following specific steps:
step 1: subjecting the NiX to2Mixing the polyimide and the mixture, and mechanically grinding the mixture to obtain reactant powder;
step 2: dispersing and dissolving the reactant powder in a solvent to obtain a mixed solution, and carrying out organic-inorganic hybrid reaction to obtain a reactant precursor solution;
and step 3: and evaporating the reactant precursor solution at constant temperature to obtain colorimetric humidity sensitive material powder.
Preferably, the NiX2And the polyimide is in a mass ratio of (0.001-10): 1.
more preferably, the NiX2And the polyimide is in a mass ratio of (0.1-1): 1.
preferably, the mechanical grinding process is carried out at 20-160 ℃ for 0.1-6 h.
Preferably, the solvent comprises butyrolactone, dimethylacetamide, N-methylpyrrolidone or N, N-dimethylformamide.
More preferably, the solvent is dimethylacetamide or N, N-dimethylformamide.
Preferably, the total concentration of the reactant powder in the mixed solution is 0.1-6 mol/L.
More preferably, the total concentration of the reactant powder in the mixed solution is 0.2-0.6 mol/L.
Preferably, the temperature of the organic-inorganic hybrid reaction is 60-300 ℃, and the time is 1-36 h.
More preferably, the temperature of the organic-inorganic hybrid reaction is 60-120 ℃, and the time is 6-12 h.
Preferably, the organic-inorganic hybrid reaction is carried out under stirring conditions.
A colorimetric humidity sensor comprises an electrode substrate and a humidity sensitive material layer which are arranged in a laminated manner; the humidity sensitive material layer adopts the colorimetric humidity sensitive material.
Preferably, the thickness of the humidity sensitive material layer is 10-6000 nm.
More preferably, the humidity sensitive material layer is formed by the colorimetric humidity sensitive material, and the thickness is 100-300 nm.
Preferably, the electrode substrate comprises FTO conductive glass or interdigitated electrodes.
According to the technical scheme, compared with the prior art, the invention discloses and provides the colorimetric moisture-sensitive material and the preparation method and application thereof, wherein the colorimetric moisture-sensitive material is prepared from Polyimide (PI) and nickel halide (NiX)2) Is prepared as a raw material. PI as organic ligand in organic-inorganic hybrid material, NiX2As inorganic ligand, prepared PI-NiX2The colorimetric humidity sensitive material has the high stability of polyimide and the high sensitivity and humidity sensing performance of nickel halide, can be used in harsh environments such as high temperature and low temperature, and has high irradiation resistance because the polyimide has excellent irradiation resistance, so that the colorimetric humidity sensitive material provided by the invention has higher irradiation resistance. The sensor obtained based on the colorimetric humidity-sensitive material has excellent colorimetric humidity-sensitive performance at the temperature of-80-300 ℃ and the RH of 0-95 percent, is not easy to deliquesce and lose efficacy, and hasHigh environmental stability, no heavy metal and organic components harmful to the environment, environmental protection and the like, and can be expected to have wide application prospect in agricultural production, information sensing, and special industrial fields such as nuclear industry, military industry and the like.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, it is obvious that the drawings in the following description are only embodiments of the present invention, and for those skilled in the art, other drawings can be obtained according to the provided drawings without creative efforts.
FIG. 1 is a schematic diagram of a colorimetric humidity sensor according to the present invention;
FIG. 2 is an XRD pattern of the organic-inorganic hybrid colorimetric humidity-sensitive material prepared in example 1 provided by the present invention;
FIG. 3 is a graph comparing characteristic colors of colorimetric humidity sensors prepared in example 1 in 11%, 33%, 52%, 75% and 95% RH atmospheres provided by the present invention;
FIG. 4 is a thermogravimetric plot of the organic-inorganic hybrid colorimetric humidity-sensitive material prepared in example 1 provided by the present invention;
FIG. 5 is a response recovery curve at a 10Hz operating frequency for a colorimetric humidity sensor made in accordance with example 1 provided herein;
FIG. 6 is an enlarged view of the response recovery curve at 10Hz operating frequency for the colorimetric humidity sensor prepared in example 1 provided by the present invention;
FIG. 7 is a hysteresis curve of a colorimetric humidity sensor made in accordance with example 1 at a 10Hz operating frequency as provided by the present invention.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The embodiment of the invention discloses a colorimetric humidity-sensitive material, which comprises polyimide and NiX2(ii) a Wherein X in the formula is selected from I, Cl and Br.
In order to further optimize the above technical solution, NiX2The purity of (A) is greater than or equal to 99.5%, and the purity of PI is greater than or equal to 98%.
A method for preparing a colorimetric humidity-sensitive material comprises the following specific steps:
s1: mixing NiX2Mixing with polyimide, and mechanically grinding to obtain reactant powder;
s2: dispersing and dissolving the reactant powder in a solvent to obtain a mixed solution, and carrying out organic-inorganic hybrid reaction to obtain a reactant precursor solution;
s3: and (4) evaporating the precursor solution of the reactant at constant temperature to obtain colorimetric humidity sensitive material powder.
In order to further optimize the above technical solution, NiX2And polyimide in a mass ratio of (0.001-10): 1.
in order to further optimize the above technical solution, NiX2And polyimide in a mass ratio of (0.1-1): 1.
in order to further optimize the technical scheme, the mechanical grinding process is carried out at the temperature of 20-160 ℃ for 0.1-6 h.
In order to further optimize the technical scheme, NiX is used for obtaining reactant powder2And PI is mechanically ground for 2-4 h at the temperature of 60-95 ℃.
In order to further optimize the above technical solution, the solvent comprises butyrolactone, dimethylacetamide, N-methylpyrrolidone or N, N-dimethylformamide.
In order to further optimize the above technical solution, the purity of the solvent is 95% of chromatographic grade.
In order to further optimize the technical scheme, the solvent is dimethylacetamide or N, N-dimethylformamide.
In order to further optimize the technical scheme, the total concentration of reactant powder in the mixed solution is 0.1-6 mol/L.
In order to further optimize the technical scheme, the total concentration of reactant powder in the mixed solution is 0.2-0.6 mol/L.
In order to further optimize the technical scheme, the temperature of the organic-inorganic hybrid reaction is 60-300 ℃, and the time is 1-36 h.
In order to further optimize the technical scheme, the temperature of the organic-inorganic hybrid reaction is 80-110 ℃, and the time is 6-10 h.
In order to further optimize the technical scheme, the organic-inorganic hybrid reaction is carried out under the stirring condition.
In order to further optimize the technical scheme, the stirring is magnetic stirring.
A colorimetric humidity sensor comprises an electrode substrate 2 and a humidity sensitive material layer 1 which are arranged in a laminated manner; the humidity sensitive material layer 1 adopts a colorimetric humidity sensitive material.
In order to further optimize the technical scheme, the thickness of the humidity sensitive material layer 1 is 10-6000 nm.
In order to further optimize the technical scheme, the humidity sensitive material layer 1 is made of a colorimetric humidity sensitive material, and the thickness of the humidity sensitive material layer is 100-300 nm.
In order to further optimize the above technical solution, the electrode substrate 2 is FTO conductive glass or an interdigital electrode.
A method of making a colorimetric humidity sensor comprising the steps of:
s1: preparing a dispersion solution by using a colorimetric humidity-sensitive material, and pretreating an electrode substrate 2 by using FTO conductive glass as an electrode substrate;
s2: attaching the dispersion liquid to the single surface of the pretreated electrode substrate 2;
s3: and (4) annealing treatment is carried out, and a humidity sensitive material layer is formed on one side of the electrode substrate 2, so that the colorimetric humidity sensor is obtained.
In order to further optimize the technical scheme, the annealing temperature is 60-130 ℃, and the time is 1.0-1.5 h.
In order to further optimize the technical scheme, the temperature of the annealing treatment is preferably 80 ℃, and the time is 1 h.
In order to further optimize the above technical solution, the pretreatment process of the electrode substrate 2 is as follows:
s11: cleaning the FTO conductive glass for 15min by using conductive glass cleaning solution, deionized water, acetone and isopropanol in sequence;
s12: blowing the cleaned FTO conductive glass by using nitrogen;
s13: and treating the FTO conductive glass for 20min by using an ultraviolet ozone cleaning machine so as to improve the wettability of the electrode substrate 2.
In order to further optimize the technical scheme, the dispersion liquid is obtained by mixing the colorimetric humidity-sensitive material and a dispersion solvent;
in order to further optimize the technical scheme, the dispersion liquid is attached to one side of the electrode substrate 2 in a spin coating or screen printing mode, the spin coating rotating speed is 1200-5000 rpm, and the time is 20-40 s.
In order to further optimize the technical scheme, the dispersion liquid is attached to one side of the electrode substrate 2 in a spin coating or screen printing mode, the spin coating rotating speed is 1200-2800 rpm, and the time is 25-35 s.
In order to further optimize the technical scheme, the dispersion liquid is attached to one side of the electrode substrate 2 by adopting a spin coating or screen printing mode, the spin coating rotating speed is 1800rpm, and the time is 30 s.
In order to further optimize the technical scheme, the colorimetric humidity sensor is prepared by adopting a spin coating or molding method. The molding method is to pour the polyimide-nickel iodide solution into the film, and heat and cool the film to obtain the colorimetric humidity sensor.
Example 1
10mg of anhydrous nickel iodide (NiI)299.5%) and 100mg of polyimide (PI, 98% purity, water-soluble polyimide, type 5218 dupont, usa), mechanically grinding at 85 ℃ for 4h, mixing the obtained mixed powder with 10m L N, N-dimethylformamide (N, N-dimethylformamide, chromatographic grade 95%), and magnetically stirring at 90 ℃ for 10h to perform organic-inorganic hybrid reaction to obtain a reaction product;
cleaning the FTO conductive glass for 20min by using conductive glass cleaning solution, deionized water, acetone and isopropanol in sequence, then blow-drying by using nitrogen, and then treating for 40min by using an ultraviolet ozone cleaning machine to obtain pretreated FTO conductive glass;
and dripping 100 mu L of a reaction product system onto the single side of the pretreated FTO conductive glass, spin-coating for 30s at 1800rpm, then carrying out annealing treatment for 1h at 85 ℃, and forming a humidity sensitive material layer (with the thickness of 400nm) on the single side of the electrode substrate to obtain the colorimetric humidity sensor.
Removing the solvent in the organic-inorganic hybrid reaction product system to obtain a colorimetric humidity sensitive material; XRD characterization of the comparative color humidity sensitive material was performed, and the results are shown in FIG. 2. XRD data in figure 2 shows that the colorimetric humidity sensitive material is polyimide-nickel iodide organic-inorganic hybrid material (PI-NiI)2)。
The performance test of the colorimetric humidity sensor is as follows:
the colorimetric humidity sensors were placed in clear glass vials at 11%, 33%, 52%, 75% and 95% RH (relative humidity), respectively, and the surface color of the colorimetric humidity sensors was recorded by photographing. As shown in fig. 3, the colorimetric humidity sensors are respectively gray black, red brown, dark yellow, light yellow and light white in 11%, 33%, 52%, 75% and 95% RH atmospheres, which indicates that the colorimetric humidity sensors have distinct and prominent colors in different humidity ranges.
Performing a thermal weight loss test on the color and humidity sensitive material in a nitrogen environment, wherein the temperature range is 20-350 ℃. As can be seen from fig. 4, at <100 ℃, the adsorbed water molecules in the material are removed, showing the first weight loss change in the curve. The weight of the material is unchanged in a test temperature range of 100-350 ℃, and the result shows that the temperature stability of the material is excellent, and the performance of the material is unchanged in a temperature range of 20-350 ℃.
The colorimetric humidity sensor is placed in the atmosphere of 11%, 33%, 52%, 75% and 95% RH in sequence at the working frequency of 10Hz, the impedance value of the colorimetric humidity sensor under the corresponding condition is tested, and the response recovery curve of the device is obtained, and the result is shown in fig. 5. Meanwhile, fig. 6 shows that the response time of the colorimetric humidity sensor is less than 1s and the recovery time is about 150s, and it can be seen from fig. 5 and 6 that the colorimetric humidity sensor shows very high response sensitivity and has an advantage of fast response compared to other colorimetric humidity sensors.
At the working frequency of 10Hz, the colorimetric humidity sensor is sequentially placed in the atmosphere with different relative humidity for adsorption (the colorimetric humidity sensor is placed from low humidity to high humidity) and desorption (the colorimetric humidity sensor is placed from high humidity to low humidity), so that the impedance values of the colorimetric humidity sensor in the atmosphere of 11%, 33%, 52%, 75% and 95% RH are sequentially obtained, and the hysteresis curve of the colorimetric humidity sensor at the working frequency of 10Hz is obtained, and the result is shown in fig. 7. It can be known that the moisture hysteresis of the colorimetric humidity sensor is close to 0 in the range of 0-70% RH, and the overall moisture hysteresis of the device is less than 5%.
Example 2
60mg of anhydrous nickel iodide (NiI)299.5%) and 100mg of polyimide (PI, 98% purity, water-soluble polyimide, type 5218 dupont, usa), mechanically grinding at 85 ℃ for 4h, mixing the obtained mixed powder with 10m L N, N-dimethylformamide (N, N-dimethylformamide, chromatographic grade 95%), and magnetically stirring at 90 ℃ for 10h to perform organic-inorganic hybrid reaction to obtain a reaction product;
cleaning the FTO conductive glass for 20min by using conductive glass cleaning solution, deionized water, acetone and isopropanol in sequence, then blow-drying by using nitrogen, and then treating for 40min by using an ultraviolet ozone cleaning machine to obtain pretreated FTO conductive glass;
and dripping 100 mu L of a reaction product system onto the single side of the pretreated FTO conductive glass, spin-coating for 30s at 1800rpm, then carrying out annealing treatment for 1h at 85 ℃, and forming a humidity sensitive material layer (with the thickness of 400nm) on the single side of the electrode substrate to obtain the colorimetric humidity sensor.
The performance of the colorimetric moisture sensor was tested according to the method of example 1, and the results were substantially the same as example 1.
Example 3
30mg of anhydrous nickel iodide (NiI)299.5% purity) and 100mg of polyimide (PI, 98% purity, water-soluble polyimide, USA)5218 DuPont company), mechanically grinding at 85 ℃ for 4h, mixing the obtained mixed powder with 10m L N, N-dimethylformamide (N, N-dimethylformamide, 95% in chromatographic grade), and magnetically stirring at 90 ℃ for 10h to perform organic-inorganic hybrid reaction to obtain a reaction product;
cleaning the FTO conductive glass for 20min by using conductive glass cleaning solution, deionized water, acetone and isopropanol in sequence, then blow-drying by using nitrogen, and then treating for 40min by using an ultraviolet ozone cleaning machine to obtain pretreated FTO conductive glass;
and dripping 100 mu L of a reaction product system onto the single side of the pretreated FTO conductive glass, spin-coating for 30s at 1800rpm, then carrying out annealing treatment for 1h at 85 ℃, and forming a humidity sensitive material layer (with the thickness of 400nm) on the single side of the electrode substrate to obtain the colorimetric humidity sensor.
The performance of the colorimetric moisture sensor was tested according to the method of example 1, and the results were substantially the same as example 1.
The colorimetric humidity-sensitive material provided by the invention has the characteristic of colorimetric humidity-sensitive and is environment-friendly; the adopted raw materials have wide sources and low price; the colorimetric humidity sensor is prepared by a mechanochemical method, is simple to operate and environment-friendly, has the advantages of simple process equipment, low cost and short preparation period when being prepared by the colorimetric humidity-sensitive material, is easy for industrial production and has good application prospect.
The embodiments in the present description are described in a progressive manner, each embodiment focuses on differences from other embodiments, and the same and similar parts among the embodiments are referred to each other. The device disclosed by the embodiment corresponds to the method disclosed by the embodiment, so that the description is simple, and the relevant points can be referred to the method part for description.
The previous description of the disclosed embodiments is provided to enable any person skilled in the art to make or use the present invention. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other embodiments without departing from the spirit or scope of the invention. Thus, the present invention is not intended to be limited to the embodiments shown herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.
Claims (10)
1. A colorimetric humidity-sensitive material comprising polyimide and NiX2(ii) a Wherein X in the formula is selected from I, Cl and Br.
2. A method for preparing a colorimetric moisture-sensitive material as claimed in claim 1, comprising the following specific steps:
step 1: subjecting the NiX to2Mixing the polyimide and the mixture, and mechanically grinding the mixture to obtain reactant powder;
step 2: dispersing and dissolving the reactant powder in a solvent to obtain a mixed solution, and carrying out organic-inorganic hybrid reaction to obtain a reactant precursor solution;
and step 3: and evaporating the reactant precursor solution at constant temperature to obtain colorimetric humidity sensitive material powder.
3. A method of preparing a colorimetric moisture-sensitive material as claimed in claim 2, wherein the NiX is2And the polyimide is in a mass ratio of (0.001-10): 1.
4. the method of claim 2, wherein the mechanical milling is performed at 20 to 160 ℃ for 0.1 to 6 hours.
5. A method of preparing a colorimetric moisture-sensitive material as claimed in claim 2, wherein the solvent comprises butyrolactone, dimethylacetamide, N-methylpyrrolidone or N, N-dimethylformamide.
6. The method of preparing a colorimetric moisture-sensitive material according to claim 2, wherein the total concentration of the reactant powder in the mixed solution is 0.1 to 6 mol/L.
7. The method for preparing a colorimetric humidity-sensitive material according to claim 2, wherein the temperature of the organic-inorganic hybrid reaction is 60 to 300 ℃ and the time is 1 to 36 hours.
8. A colorimetric humidity sensor obtained from a colorimetric humidity-sensitive material according to claim 1, comprising an electrode substrate (2) and a humidity-sensitive material layer (1) which are disposed in a stack; the humidity sensitive material layer (1) adopts the colorimetric humidity sensitive material.
9. A colorimetric humidity sensor according to claim 8, wherein the humidity sensitive material layer (1) has a thickness of 10 to 6000 nm.
10. Colorimetric humidity sensor according to claim 8, characterized in that the electrode substrate (2) is FTO conductive glass or an interdigitated electrode.
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