CN109613071B - Humidity sensor of humidity-sensitive composite membrane based on polylysine modified carbon-based material and preparation method thereof - Google Patents
Humidity sensor of humidity-sensitive composite membrane based on polylysine modified carbon-based material and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a humidity sensor of a humidity-sensitive composite membrane based on polylysine modified carbon-based materials and a preparation method thereof. The preparation method comprises the following steps: preprocessing a sensitive device; preparing polylysine dispersion liquid, and preparing carbon-series material dispersion liquid; and preparing a single-layer or multi-layer humidity-sensitive composite film on a sensitive device by using the prepared polylysine dispersion liquid and the carbon-based material dispersion liquid, and finally drying to obtain the humidity sensor based on the humidity-sensitive composite film of the polylysine modified carbon-based material. The invention can solve the problems of poor response, low recovery speed and the like of the single carbon material humidity sensor and enhance the humidity sensitivity of the single carbon material humidity sensor.
Description
Technical Field
The invention belongs to the technical field of sensitive electronics and composite nano materials, and particularly relates to a humidity sensor based on a humidity-sensitive composite membrane of polylysine modified carbon-based materials and a preparation method thereof.
Background
Human survival and social activities are closely related to humidity, and humidity sensors are widely applied to agriculture, human health detection and industrial environment monitoring. The development of humidity sensitive materials has been through three stages, from early electrolyte humidity sensors, to semiconductor ceramic humidity sensors, to organic polymer humidity sensors. Although the organic polymer material contains abundant functional groups and can provide a large number of adsorption sites for water molecules, the organic polymer material alone serving as the humidity sensitive material has the defects of poor conductivity, large humidity stagnation, poor stability and the like. In recent years, carbon-based materials including graphene, carbon nanotubes, carbon nanofibers, and the like have been widely used in the field of humidity sensors. However, since a single carbon-based material is difficult to be used alone in a humidity sensor due to its excellent conductivity and poor hydrophilicity, a chemical modification method of an organic material is commonly used to improve the humidity-sensitive property of the carbon-based material. For example, the invention patent with application number 201010142768.4 discloses a preparation method of a humidity sensor based on graphene composite. According to the invention, the good hygroscopicity of polyvinylpyrrolidone and the conductivity of reduced graphene oxide are utilized, and polyvinylpyrrolidone is used for modifying graphene to prepare the resistance type humidity sensor based on the polyvinylpyrrolidone-graphene conductive composite film. For example, the invention patent with application number 201710776189.7 discloses a humidity sensor and a method for making the same. The humidity sensing layer is made of graphene oxide or carbon oxide nano tube composite perfluorinated sulfonic acid or sulfonated polyether ether ketone organic materials, and under the action of the two materials, a humidity sensor with high linearity in humidity response can be complemented.
Polylysine is a water-soluble high-molecular organic material, has weak conductivity and rich hydrophilic functional groups (amino, imino and carbon), can be used as a moisture-sensitive modification material with strong hydrophilicity to provide more adsorption sites for water molecules, and is not developed and utilized in the field of humidity sensors at present.
Disclosure of Invention
The invention aims to: the humidity sensor of the humidity-sensitive composite membrane based on the polylysine modified carbon-based material and the preparation method thereof are provided, and the problems of poor response, low recovery speed and the like of a single carbon material humidity sensor are solved, so that the humidity sensitivity of the single carbon-based material humidity sensor is enhanced.
The technical scheme adopted by the invention is as follows:
the humidity sensor of the humidity-sensitive composite membrane based on the polylysine modified carbon-based material comprises a sensitive device and the humidity-sensitive composite membrane arranged on the sensitive device, wherein the humidity-sensitive composite membrane is made of the polylysine modified carbon-based material.
The carbon-based material is one or a combination of several of carbon-based materials such as a single-walled carbon nanotube, a multi-walled carbon nanotube, graphene in the form of quantum dots, nanosheets, nanodiscs or nanowires, graphene oxide, reduced graphene oxide, carbon nanofibers, C60, graphite, nanoporous carbon and functionalized carbon materials.
The functionalized carbon material is one or a combination of several of carbon materials such as aminated graphene, hydroxylated graphene, carboxylated graphene, fluorinated graphene, thinned graphene, aminated graphene oxide, hydroxylated graphene oxide, carboxylated graphene oxide, fluorinated graphene oxide, thinned graphene oxide, aminated reduced graphene oxide, hydroxylated reduced graphene oxide, carboxylated reduced graphene oxide, fluorinated reduced graphene oxide, thinned reduced graphene oxide and the like.
Wherein the sensitive device is one of an interdigital electrode with a flexible or rigid substrate and a Quartz Crystal Microbalance (QCM) device.
Wherein, the thickness of the humidity-sensitive composite membrane is 50nm-50 μm.
The preparation method of the humidity sensor based on the humidity-sensitive composite membrane of the polylysine modified carbon-based material comprises the following steps:
preprocessing a sensitive device;
preparing polylysine dispersion liquid and preparing carbon-series material dispersion liquid;
preparing a single-layer or multi-layer humidity-sensitive composite film on a sensitive device by the polylysine dispersion liquid and the carbon-based material dispersion liquid prepared in the step two through processes of spraying, spin coating, drop coating, ink-jet printing, electrostatic spinning, electrochemical growth or self-assembly and the like;
and finally drying to obtain the humidity sensor based on the humidity-sensitive composite membrane of the polylysine modified carbon-based material.
In the step (i), the sensitive device is an interdigital electrode with a flexible or rigid substrate or a Quartz Crystal Microbalance (QCM) device, and the pretreatment step of the sensitive device comprises: and cleaning the sensitive device in deionized water, acetone, alcohol and deionized water in sequence, and then blowing the sensitive device by using nitrogen.
In the second step, the polylysine dispersion liquid is: the solvent was a 0.01% w/v polylysine dispersion in deionized water.
In the second step, the carbon-based material is one or a combination of several of single-walled carbon nanotubes, multi-walled carbon nanotubes, graphene in the form of quantum dots, nanosheets, nanodisks or nanowires, graphene oxide, reduced graphene oxide, carbon nanofibers, C60, graphite, nanoporous carbon, functionalized carbon materials and the like.
The functionalized carbon material is one or a combination of several of carbon materials such as aminated graphene, hydroxylated graphene, carboxylated graphene, fluorinated graphene, thinned graphene, aminated graphene oxide, hydroxylated graphene oxide, carboxylated graphene oxide, fluorinated graphene oxide, thinned graphene oxide, aminated reduced graphene oxide, hydroxylated reduced graphene oxide, carboxylated reduced graphene oxide, fluorinated reduced graphene oxide, thinned reduced graphene oxide and the like.
In summary, due to the adoption of the technical scheme, the invention has the beneficial effects that:
the invention provides a humidity sensor based on a polylysine modified carbon-based humidity-sensitive composite membrane and a preparation method thereof, and the humidity sensor has universality in the field of carbon-based material humidity sensors. The polylysine is used as a modification material to be combined with the carbon-based material to form a new nano composite material system, so that the excellent mechanical, electrical and chemical properties and large specific surface area characteristics of the carbon-based material are fully exerted, and meanwhile, rich hydrophilic functional groups can be provided, more adsorption sites are provided for water molecules, and the humidity sensitivity of the composite material is improved. In addition, due to the biocompatibility of the polylysine and the carbon-based material, the method for modifying the carbon material by the polylysine can be further applied to human health detection, and has the advantages of no toxicity, greenness and fitting.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings needed to be used in the embodiments will be briefly described below, it should be understood that the following drawings only illustrate some embodiments of the present invention and therefore should not be considered as limiting the scope, and for those skilled in the art, other related drawings can be obtained according to the drawings without inventive efforts.
FIG. 1 is a schematic view of the molecular structure of polylysine according to the present invention;
FIG. 2 is a field emission scanning electron microscope (FE-SEM) image of a film of pure multi-walled carbon nanotubes;
FIG. 3 is a field emission scanning electron microscope (FE-SEM) image of the polylysine/multiwall carbon nanotube composite film according to the present invention;
FIG. 4 is an X-ray photoelectron spectroscopy (XPS) analysis of a pure multi-walled carbon nanotube film at C1 s;
FIG. 5 is an X-ray photoelectron spectroscopy (XPS) plot of a polylysine/multiwall carbon nanotube composite film according to the present invention at C1 s;
FIG. 6 is an X-ray photoelectron spectroscopy (XPS) plot of a polylysine/multiwall carbon nanotube composite film on N1s according to the present invention;
FIG. 7 is a graph showing the real-time resistance change at different relative humidities for a pure multi-walled carbon nanotube film prepared according to the present invention;
FIG. 8 is a graph showing the real-time resistance change of the polylysine/multiwall carbon nanotube composite film prepared according to the present invention at different relative humidities.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is described in further detail below with reference to the accompanying drawings and embodiments. It should be understood that the detailed description and specific examples, while indicating the preferred embodiment of the invention, are intended for purposes of illustration only and are not intended to limit the scope of the invention.
Thus, the following detailed description of the embodiments of the present invention, presented in the figures, is not intended to limit the scope of the invention, as claimed, but is merely representative of selected embodiments of the invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments of the present invention without making any creative effort, shall fall within the protection scope of the present invention.
It is noted that relational terms such as "first" and "second," and the like, may be used solely to distinguish one entity or action from another entity or action without necessarily requiring or implying any actual such relationship or order between such entities or actions. Also, the terms "comprises," "comprising," or any other variation thereof, are intended to cover a non-exclusive inclusion, such that a process, method, article, or apparatus that comprises a list of elements does not include only those elements but may include other elements not expressly listed or inherent to such process, method, article, or apparatus. Without further limitation, an element defined by the phrase "comprising an … …" does not exclude the presence of other identical elements in a process, method, article, or apparatus that comprises the element.
In order to solve the problems of poor response, low recovery speed and the like of a single carbon material humidity sensor and further enhance the humidity sensitivity performance of the single carbon material humidity sensor, the invention provides a humidity sensor based on a polylysine modified carbon material humidity-sensitive composite film, which comprises a sensitive device and a humidity-sensitive composite film arranged on the sensitive device, wherein the humidity-sensitive composite film is made of polylysine modified carbon material. The carbon material is one or a combination of more of single-walled carbon nanotubes, multi-walled carbon nanotubes, graphene in the form of quantum dots, nanosheets, nanodiscs or nanowires, graphene oxide, reduced graphene oxide, carbon nanofibers, C60, graphite, nanoporous carbon, functionalized carbon materials and other carbon materials; the functionalized carbon material is one or a combination of more of carbon materials such as aminated graphene, hydroxylated graphene, carboxylated graphene, fluorinated graphene, thinned graphene, aminated graphene oxide, hydroxylated graphene oxide, carboxylated graphene oxide, fluorinated graphene oxide, thinned graphene oxide, aminated reduced graphene oxide, hydroxylated reduced graphene oxide, carboxylated reduced graphene oxide, fluorinated reduced graphene oxide, thinned reduced graphene oxide and the like; the sensitive device is one of an interdigital electrode with a flexible or rigid substrate and a Quartz Crystal Microbalance (QCM) device; the thickness of the humidity-sensitive composite membrane is 50nm-50 μm. The polylysine dispersion liquid and the carbon-based material dispersion liquid are used for preparing a single-layer or multi-layer humidity-sensitive composite film on a sensitive device through processes of spraying, spin coating, drop coating, ink-jet printing, electrostatic spinning, electrochemical growth or self-assembly and the like.
The preparation method of the humidity sensor based on the humidity-sensitive composite membrane of the polylysine modified carbon-based material comprises the following steps:
preprocessing a sensitive device;
in the step (i), the sensitive device is an interdigital electrode with a flexible or rigid substrate or a Quartz Crystal Microbalance (QCM) device, and the pretreatment step of the sensitive device comprises: and cleaning the sensitive device in deionized water, acetone, alcohol and deionized water in sequence, and then blowing the sensitive device by using nitrogen.
Preparing polylysine dispersion liquid and preparing carbon-series material dispersion liquid;
the polylysine dispersion is: the solvent is deionized water, polylysine dispersion with the concentration of 0.01 percent w/v; the carbon material is one or a combination of more of single-walled carbon nanotubes, multi-walled carbon nanotubes, graphene in the form of quantum dots, nanosheets, nanodiscs or nanowires, graphene oxide, reduced graphene oxide, carbon nanofibers, C60, graphite, nanoporous carbon, functionalized carbon materials and other carbon materials; the functionalized carbon material is one or a combination of more of carbon materials such as aminated graphene, hydroxylated graphene, carboxylated graphene, fluorinated graphene, thinned graphene, aminated graphene oxide, hydroxylated graphene oxide, carboxylated graphene oxide, fluorinated graphene oxide, thinned graphene oxide, aminated reduced graphene oxide, hydroxylated reduced graphene oxide, carboxylated reduced graphene oxide, fluorinated reduced graphene oxide, thinned reduced graphene oxide and the like.
Preparing a single-layer or multi-layer humidity-sensitive composite film on a sensitive device by the polylysine dispersion liquid and the carbon-based material dispersion liquid prepared in the step two through processes of spraying, spin coating, drop coating, ink-jet printing, electrostatic spinning, electrochemical growth or self-assembly and the like;
fourthly, drying to obtain the humidity sensor of the humidity sensitive composite membrane based on the polylysine modified carbon-based material;
the drying conditions are as follows: drying at 60 deg.C for 12 hr.
The features and properties of the present invention are described in further detail below with reference to examples.
Example 1
The sensing device selected in the embodiment is an interdigital electrode, the interdigital electrode is a gold electrode manufactured on a flexible PI substrate, the interdigital distance of the interdigital electrode is 200 μm, the interdigital width of the interdigital electrode is 200 μm, and the electrode thickness of the interdigital electrode is 100 nm; the carbon-based material selected in the embodiment is a multi-walled carbon nanotube, and the specific process steps are as follows:
(1) preparing a flexible interdigital electrode of the PI substrate, and cutting the flexible PI substrate by using a cutting machine, wherein the cutting specification is 15 multiplied by 15 mm; placing the cut PI substrate on a substrate frame, sequentially cleaning in detergent, deionized water, acetone, alcohol and deionized water, carrying out ultrasonic treatment for 15-30 minutes in each cleaning process, and then blowing and drying by using nitrogen; vapor plating gold interdigital electrodes on the PI substrate;
(2) preparing polylysine dispersion liquid, wherein a solvent is deionized water, and the polylysine dispersion liquid with the concentration of 0.01% w/v is prepared; preparing a multiwalled carbon nanotube dispersion liquid, measuring a certain dose of multiwalled carbon nanotube dispersion liquid with the concentration of 2 wt% at room temperature, diluting the multiwalled carbon nanotube dispersion liquid by 200 times with deionized water, and carrying out ultrasonic treatment for later use;
(3) mixing the polylysine dispersion liquid obtained in the step (2) with the multi-wall carbon nanotube solution according to the weight ratio of 1: 1, and stirring and ultrasonic treatment are assisted to form a uniform mixed solution; preparing a composite sensitive film on an interdigital electrode of a flexible PI substrate by a drop coating process through a mixed solution of polylysine and a multi-walled carbon nanotube;
(4) and drying for 12 hours at the temperature of 60 ℃ to obtain the humidity sensor based on the humidity-sensitive composite membrane of the polylysine modified multi-walled carbon nanotube.
Example 2
The sensitive device selected in the embodiment is an interdigital electrode, the interdigital electrode is a silver electrode of a silicon substrate, the interdigital distance of the interdigital electrode is 50 μm, the interdigital width of the interdigital electrode is 50 μm, and the electrode thickness of the interdigital electrode is 50 nm; the carbon-based material selected in the embodiment is graphene, and the specific process steps are as follows:
(1) cleaning silicon substrate interdigital electrodes in deionized water, acetone, alcohol and deionized water in sequence, and then blowing the silicon substrate interdigital electrodes by using nitrogen;
(2) preparing polylysine dispersion liquid, wherein a solvent is deionized water, and the polylysine dispersion liquid with the concentration of 0.01% w/v is prepared; preparing graphene dispersion liquid, measuring a certain amount of graphene dispersion liquid with the concentration of 2mg/ml at room temperature, diluting the graphene dispersion liquid by 200 times with deionized water, and performing ultrasonic treatment for later use;
(3) depositing a graphene film on the silver interdigital electrode by using the polylysine dispersion liquid and the graphene dispersion liquid in the step (2) through a spraying process, drying for 2 hours, and then depositing a polylysine film on the graphene film;
(4) and drying for 12 hours at the temperature of 60 ℃ to obtain the humidity sensor based on the humidity-sensitive composite membrane of polylysine modified graphene.
Example 3
The sensing device selected in the embodiment is a Quartz Crystal Microbalance (QCM) device, and the upper and lower metal electrodes of the Quartz Crystal Microbalance (QCM) device are silver electrodes, and the fundamental frequency of the quartz crystal microbalance is 9.98 MHz; the carbon-based material selected in the embodiment is graphene oxide, and the specific process steps are as follows:
(1) cleaning a Quartz Crystal Microbalance (QCM) device in deionized water, acetone, alcohol and deionized water in sequence, and then blowing the quartz crystal microbalance device by using nitrogen;
(2) preparing polylysine dispersion liquid, wherein a solvent is deionized water, and the polylysine dispersion liquid with the concentration of 0.01% w/v is prepared; preparing a graphene oxide dispersion liquid, measuring a certain amount of the graphene oxide dispersion liquid at room temperature, diluting to a concentration of 0.2mg/ml, and performing ultrasonic treatment for later use;
(3) respectively depositing polylysine films on the two surfaces of an upper metal electrode and a lower metal electrode of a Quartz Crystal Microbalance (QCM) device by using the polylysine dispersion liquid and the graphene oxide dispersion liquid in the step (2) through a spraying process, drying for 2 hours, and then depositing a graphene oxide film to form a composite sensitive film;
(4) and drying for 12 hours at the temperature of 60 ℃ to obtain the humidity sensor based on the humidity-sensitive composite membrane of polylysine modified graphene oxide.
Example 4
The sensitive device selected in the embodiment is a Quartz Crystal Microbalance (QCM) device, wherein upper and lower metal electrodes of the Quartz Crystal Microbalance (QCM) device are gold electrodes, and the fundamental frequency of the quartz crystal microbalance is 9.98 MHz; the carbon-based material selected in the embodiment is reduced graphene oxide, and the specific process steps are as follows:
(1) cleaning a Quartz Crystal Microbalance (QCM) device in deionized water, acetone, alcohol and deionized water in sequence, and then blowing the quartz crystal microbalance device by using nitrogen;
(2) preparing polylysine dispersion liquid, wherein a solvent is deionized water, and the polylysine dispersion liquid with the concentration of 0.01% w/v is prepared; preparing reduced graphene oxide dispersion liquid, measuring a certain amount of reduced graphene oxide dispersion liquid at room temperature, diluting to a concentration of 0.5mg/ml, and performing ultrasonic treatment for later use;
(3) respectively depositing reduced graphene oxide films on two surfaces of an upper electrode and a lower electrode of a Quartz Crystal Microbalance (QCM) device by using the polylysine dispersion liquid and the reduced graphene oxide dispersion liquid in the step (2) through a spraying process, drying for 2 hours, and then depositing the polylysine films to form a composite sensitive film;
(4) and drying for 12 hours at the temperature of 60 ℃ to obtain the humidity sensor based on the humidity-sensitive composite membrane of polylysine modified graphene oxide.
Comparative example 1
The sensing device selected in the embodiment is an interdigital electrode, the interdigital electrode is a gold electrode manufactured on a flexible PI substrate, the interdigital distance of the interdigital electrode is 200 μm, the interdigital width of the interdigital electrode is 200 μm, and the electrode thickness of the interdigital electrode is 100 nm; the carbon-based material selected in the embodiment is a multi-walled carbon nanotube, and the specific process steps are as follows:
(1) preparing a flexible interdigital electrode of the PI substrate, and cutting the flexible PI substrate by using a cutting machine, wherein the cutting specification is 15 multiplied by 15 mm; placing the cut PI substrate on a substrate frame, sequentially cleaning in detergent, deionized water, acetone, alcohol and deionized water, carrying out ultrasonic treatment for 15-30 minutes in each cleaning process, and then blowing and drying by using nitrogen; vapor plating gold interdigital electrodes on the PI substrate;
(2) preparing a multiwalled carbon nanotube dispersion liquid, measuring a certain dose of multiwalled carbon nanotube dispersion liquid with the concentration of 2 wt% at room temperature, diluting the multiwalled carbon nanotube dispersion liquid by 200 times with deionized water, and carrying out ultrasonic treatment for later use;
(3) preparing a composite sensitive film on the interdigital electrode of the flexible PI substrate by the multi-wall carbon nano tube solution in the step (2) through a dripping process;
(4) and drying for 12 hours at the temperature of 60 ℃ to obtain the humidity sensor based on the humidity-sensitive composite membrane of the polylysine modified multi-walled carbon nanotube.
FIG. 1 is a schematic view of the molecular structure of polylysine, which is shown to have hydrophilic functional groups such as amino groups, imino groups, and carbon groups in theory.
Fig. 2 is a field emission scanning electron microscope (FE-SEM) image of a pure multi-walled carbon nanotube film, and fig. 3 is a field emission scanning electron microscope (FE-SEM) image of a polylysine/multi-walled carbon nanotube composite film according to the present invention, and it can be seen from fig. 2 that the pure multi-walled carbon nanotube film is formed of smooth carbon nanotubes, and the polylysine/multi-walled carbon nanotube composite film shows a phenomenon that the multi-walled carbon nanotubes are coated with polylysine.
FIG. 4 is an X-ray photoelectron spectroscopy (XPS) analysis of a pure multi-walled carbon nanotube film at C1s, FIG. 5 is an X-ray photoelectron spectroscopy (XPS) analysis of a polylysine/multi-walled carbon nanotube composite film at C1s, FIG. 6 is an X-ray photoelectron spectroscopy (XPS) analysis of a polylysine/multi-walled carbon nanotube composite film at N1s, and it can be seen from FIG. 4 that binding energies at 284.6, 285.0 and 286.5eV correspond to C-C, C-H and C-O bonds, respectively. The C-N and C-O/C ═ O peaks in the composite film of fig. 5, compared to pure multiwall carbon nanotubes, occur near 285.7 and 286.7eV, indicating the presence of polylysine in the polylysine/multiwall carbon nanotube composite film. In FIG. 6, the binding energies of N1s at 400.2 and 401.8eV correspond to an amino (imino) group (-NH2/-NH) having hydrophilic properties and a quaternary ammonium or protonated nitrogen (-C-N), respectively+/-NH2H+). XPS analysis further confirms that polylysine has abundant hydrophilic functional groups.
Fig. 7 is a real-time resistance change curve of a pure multi-walled carbon nanotube film prepared according to the present invention at different relative humidities, and fig. 8 is a real-time resistance change curve of a polylysine/multi-walled carbon nanotube composite film prepared according to the present invention at different relative humidities. It can be observed from fig. 7 and 8 that the resistance change of the humidity sensitive response of the two humidity sensors within 0-91.5% RH shows a positive humidity coefficient. Compared with a polylysine/multi-wall carbon nanotube composite membrane humidity sensor, the pure multi-wall carbon nanotube humidity sensor has the advantages of low response value and slow recovery. The response of the polylysine/multi-walled carbon nanotube composite membrane humidity sensor is higher than that of a pure multi-walled carbon nanotube humidity sensor by 600 times under 91.5 percent RH, which shows that polylysineThe addition of the amino acid greatly improves the humidity-sensitive response of the pure multi-walled carbon nanotube. In addition, the response of the polylysine/multiwalled carbon nanotube composite membrane humidity sensor shows excellent linearity (R) in the range of 5.2% to 23.8% RH20.9990), the response is significantly increased in the range of 60.8% to 91.5% RH, and thus the switching characteristics in a high humidity state can be used to detect a high humidity environment.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents and improvements made within the spirit and principle of the present invention are intended to be included within the scope of the present invention.
Claims (8)
1. Humidity sensor based on polylysine modification carbon system material's humidity sensitive complex film, its characterized in that: the humidity-sensitive composite membrane is arranged on the sensitive device, and the material of the humidity-sensitive composite membrane is prepared by polylysine modified carbon-based material; the carbon material is one or a combination of several of a single-walled carbon nanotube, a multi-walled carbon nanotube, graphene in the form of quantum dots, nanosheets, nanodiscs or nanowires, graphene oxide, reduced graphene oxide, carbon nanofibers, C60, graphite, nanoporous carbon and a functionalized carbon material; the functionalized carbon material is one or a combination of more of aminated graphene, hydroxylated graphene, carboxylated graphene, fluorinated graphene, thinned graphene, aminated graphene oxide, hydroxylated graphene oxide, carboxylated graphene oxide, fluorinated graphene oxide, thinned graphene oxide, aminated reduced graphene oxide, hydroxylated reduced graphene oxide, carboxylated reduced graphene oxide, fluorinated reduced graphene oxide and thinned reduced graphene oxide.
2. The humidity sensor based on the humidity-sensitive composite membrane of polylysine-modified carbon-based material as claimed in claim 1, wherein: the sensitive device is one of an interdigital electrode with a flexible or rigid substrate and a quartz crystal microbalance device.
3. The humidity sensor based on the humidity-sensitive composite membrane of polylysine-modified carbon-based material as claimed in claim 1, wherein: the thickness of the humidity-sensitive composite membrane is 50nm-50 μm.
4. The preparation method of the humidity sensor based on the humidity-sensitive composite membrane of the polylysine modified carbon-based material is characterized by comprising the following steps of:
preprocessing a sensitive device;
preparing polylysine dispersion liquid and preparing carbon-series material dispersion liquid;
preparing a single-layer or multi-layer humidity-sensitive composite film on a sensitive device by the polylysine dispersion liquid and the carbon-based material dispersion liquid prepared in the step two through processes of spraying, spin coating, drop coating, ink-jet printing, electrostatic spinning, electrochemical growth or self-assembly and the like;
and finally drying to obtain the humidity sensor based on the humidity-sensitive composite membrane of the polylysine modified carbon-based material.
5. The method for preparing a humidity sensor based on the humidity-sensitive composite membrane of polylysine modified carbon-based material as claimed in claim 4, wherein: in the step I, the sensitive device is an interdigital electrode with a flexible or rigid substrate or a quartz crystal microbalance device, and the pretreatment step of the sensitive device comprises the following steps: and cleaning the sensitive device in deionized water, acetone, alcohol and deionized water in sequence, and then blowing the sensitive device by using nitrogen.
6. The method for preparing a humidity sensor based on the humidity-sensitive composite membrane of polylysine modified carbon-based material as claimed in claim 4, wherein: in the second step, the polylysine dispersion liquid is: the solvent was a 0.01% w/v polylysine dispersion in deionized water.
7. The method for preparing a humidity sensor based on the humidity-sensitive composite membrane of polylysine modified carbon-based material as claimed in claim 4, wherein: in the second step, the carbon-based material is one or a combination of several of a single-walled carbon nanotube, a multi-walled carbon nanotube, graphene in the form of quantum dots, nanosheets, nanodisks or nanowires, graphene oxide, reduced graphene oxide, carbon nanofibers, C60, graphite, nanoporous carbon and functionalized carbon material.
8. The method for preparing a humidity sensor based on the humidity-sensitive composite membrane of polylysine modified carbon-based material as claimed in claim 7, wherein: the functionalized carbon material is one or a combination of more of aminated graphene, hydroxylated graphene, carboxylated graphene, fluorinated graphene, thinned graphene, aminated graphene oxide, hydroxylated graphene oxide, carboxylated graphene oxide, fluorinated graphene oxide, thinned graphene oxide, aminated reduced graphene oxide, hydroxylated reduced graphene oxide, carboxylated reduced graphene oxide, fluorinated reduced graphene oxide and thinned reduced graphene oxide.
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