CN109613071A - The humidity sensor and preparation method thereof of wet sensitive composite membrane based on polylysine modification carbon-based material - Google Patents
The humidity sensor and preparation method thereof of wet sensitive composite membrane based on polylysine modification carbon-based material Download PDFInfo
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Abstract
The invention discloses a kind of humidity sensors and preparation method thereof of wet sensitive composite membrane based on polylysine modification carbon-based material, the humidity sensor of wet sensitive composite membrane based on polylysine modification carbon-based material includes Sensitive Apparatus and the wet sensitive composite membrane that is arranged on Sensitive Apparatus, and the material of the wet sensitive composite membrane is made by polylysine modification carbon-based material.Preparation method is the following steps are included: pre-process Sensitive Apparatus；Poly-D-lysine dispersion liquid is prepared, carbon-based material dispersion liquid is prepared；The wet sensitive composite membrane for preparing single-layer or multi-layer on Sensitive Apparatus with the poly-D-lysine dispersion liquid and carbon-based material dispersion liquid that prepare, is finally dried to obtain the humidity sensor of the wet sensitive composite membrane based on polylysine modification carbon-based material.The present invention is able to solve the problems such as single carbon material humidity sensor difference in response and slow resume speed, enhances the humidity sensitive performance of single carbon-based material humidity sensor.
Description
Technical field
The invention belongs to sensing electronics and composite nano materials technical field, repair more particularly, to based on poly-D-lysine
Adorn the humidity sensor and preparation method thereof of the wet sensitive composite membrane of carbon-based material.
Background technique
The existence and social activities of the mankind and humidity are closely related, and it is strong that humidity sensor is widely used in agricultural, human body
In health detection and industrial environment monitoring.The development of humidity-sensitive material is from the electrolyte of early stage wet successively through always three phases
Sensor is spent, develops to semiconductive ceramic humidity sensor, then arrive organic polymer humidity sensor.Though high-molecular organic material
Right functional group rich in, can provide a large amount of adsorption site, but have conduction separately as humidity-sensitive material for hydrone
Property poor, the disadvantages of humidity hysteresis is big and stability is poor.In recent years, carbon-based material includes the quilts such as graphene, carbon nanotube, carbon nano-fiber
Widely apply to humidity sensor field.However, single carbon-based material is due to its excellent electric conductivity and poor parent
It is aqueous to be difficult to be applied individually to humidity sensor, so commonly using the method for organic material chemical modification to improve carbon-based material
Wet sensitive performance.For example, application No. is 201010142768.4 patent of invention disclose it is a kind of based on the wet of graphene complex
Spend the preparation method of sensor.The invention utilizes the conduction of polyvinylpyrrolidone good hygroscopicity and redox graphene
Property, it is prepared for using polyvinyl pyrrolidon modified graphene based on polyvinylpyrrolidone-graphene conductive laminated film
Resistance type humidity sensor.For example, application No. is 201710776189.7 patent of invention disclose a kind of humidity sensor and
Preparation method.The compound perfluorinated sulfonic acid of material oxidation graphene or oxide/carbon nanometer tube or sulfonated polyether ether of the humidity inductive layer
Ketone organic material complementary can go out to have humidity response the humidity sensor of higher line degree under the action of two kinds of materials.
Poly-D-lysine is a kind of water-soluble macromolecule organic material, has weak inductive and hydrophilic functional groups abundant
(amino, imino group, carbon-based) can be used as a kind of wet sensitive decorative material that hydrophily is strong and provide more adsorption potentials for hydrone
Point is not yet developed and utilized in humidity sensor field at present.
Summary of the invention
It is an object of the invention to: the humidity sensor of the wet sensitive composite membrane based on polylysine modification carbon-based material is provided
Device and preparation method thereof, the problems such as solving single carbon material humidity sensor difference in response and slow resume speed, to enhance single
The humidity sensitive performance of carbon-based material humidity sensor.
The technical solution adopted by the invention is as follows:
The humidity sensor of wet sensitive composite membrane based on polylysine modification carbon-based material, including Sensitive Apparatus and setting
The material of wet sensitive composite membrane on Sensitive Apparatus, the wet sensitive composite membrane is made by polylysine modification carbon-based material.
Wherein, the carbon-based material is single-walled carbon nanotube, multi-walled carbon nanotube, form are quantum dot, nanometer sheet, nanometer
The graphene of disk or nano wire, graphene oxide, redox graphene, carbon nano-fiber, C60, graphite, nanoporous carbon and
The combination of one or more of the carbon-based materials such as the carbon material of function dough.
Wherein, the carbon material of the function dough is amination graphene, hydroxylating graphene, carboxylated graphene, fluorine
Graphite alkene dredges base graphite alkene, amination graphene oxide, hydroxylating graphene oxide, carboxylated graphene oxide, fluorination
Graphene oxide dredges base graphene oxide, reductive amination graphene oxide, hydroxylating redox graphene, carboxylated
One of redox graphene, fluorination carbon-based materials such as redox graphene and thin base redox graphene are several
The combination of kind.
Wherein, the Sensitive Apparatus is the interdigital electrode of flexible or rigid substrate, quartz crystal microbalance (QCM) device
It is a kind of.
Wherein, the wet sensitive composite membrane with a thickness of 50nm-50 μm.
The preparation method of the humidity sensor of wet sensitive composite membrane based on polylysine modification carbon-based material, including it is following
Step:
1. being pre-processed to Sensitive Apparatus；
2. preparing poly-D-lysine dispersion liquid, carbon-based material dispersion liquid is prepared；
3. 2. poly-D-lysine dispersion liquid and carbon-based material dispersion liquid that step is prepared pass through spraying, spin coating, drop coating, spray
The wet sensitive that the techniques such as black printing, electrostatic spinning, electrochemical growth or self assembly prepare single-layer or multi-layer on Sensitive Apparatus is compound
Film；
4. being finally dried to obtain the humidity sensor of the wet sensitive composite membrane based on polylysine modification carbon-based material.
Wherein, step 1. in, the Sensitive Apparatus is interdigital electrode, the quartz crystal microbalance of flexible or rigid substrate
(QCM) one kind of device, the pre-treatment step of the Sensitive Apparatus include: by Sensitive Apparatus successively in deionized water, acetone, wine
It cleans in essence and deionized water, is then dried up with nitrogen.
Wherein, step 2. in, poly-D-lysine dispersion liquid are as follows: solvent be deionized water 0.01%w/v concentration poly
Lysine dispersion liquid.
Wherein, step 2. in, the carbon-based material is that single-walled carbon nanotube, multi-walled carbon nanotube, form are quantum dot, receive
Rice piece, nanometer plate or nano wire graphene, graphene oxide, redox graphene, carbon nano-fiber, C60, graphite, receive
The combination of one or more of the carbon-based materials such as rice porous carbon and the carbon material of function dough.
Wherein, the carbon material of the function dough is amination graphene, hydroxylating graphene, carboxylated graphene, fluorine
Graphite alkene dredges base graphite alkene, amination graphene oxide, hydroxylating graphene oxide, carboxylated graphene oxide, fluorination
Graphene oxide dredges base graphene oxide, reductive amination graphene oxide, hydroxylating redox graphene, carboxylated
One of redox graphene, fluorination carbon-based materials such as redox graphene and thin base redox graphene are several
The combination of kind.
In conclusion by adopting the above-described technical solution, the beneficial effects of the present invention are:
In the present invention, the humidity sensor and its system of the wet sensitive composite membrane based on polylysine modification carbon-based material are proposed
Preparation Method has universality in carbon-based material humidity sensor field.Poly-D-lysine is as decorative material and carbon-based material group
New nanocomposite system is synthesized, the excellent mechanics of carbon-based material itself, electricity, chemical property and big ratio are being given full play to
While surface area characteristics, hydrophilic functional groups abundant can be provided, more adsorption sites are provided for hydrone, to improve
The wet sensitive performance of composite material.In addition, due to the biocompatibility of poly-D-lysine and carbon-based material, polylysine modification carbon
The method of material can further apply human health detection, have nontoxic, green and the advantage that can be bonded.
Detailed description of the invention
In order to illustrate the technical solution of the embodiments of the present invention more clearly, below will be to needed in the embodiment attached
Figure is briefly described, it should be understood that the following drawings illustrates only certain embodiments of the present invention, therefore is not construed as pair
The restriction of range for those of ordinary skill in the art without creative efforts, can also be according to this
A little attached drawings obtain other relevant attached drawings.
Fig. 1 is the schematic arrangement of poly-D-lysine of the present invention；
Fig. 2 is field emission scanning electron microscope (FE-SEM) figure of the film of pure multi-walled carbon nanotube；
Fig. 3 is poly-D-lysine of the present invention/multi-walled carbon nanotube composite membrane field emission scanning electron microscope (FE-
SEM) figure；
Fig. 4 is X-ray photoelectron spectroscopic analysis (XPS) analysis chart of pure multi-wall carbon nano-tube film in C1s；
Fig. 5 is x-ray photoelectron energy of the poly-D-lysine of the present invention/multi-walled carbon nanotube composite membrane on C1s
Spectrum analysis (XPS) figure；
Fig. 6 is x-ray photoelectron energy of the poly-D-lysine of the present invention/multi-walled carbon nanotube composite membrane on N1s
Spectrum analysis (XPS) figure；
Fig. 7 is that a kind of real time resistance of the pure multi-wall carbon nano-tube periosteum prepared by the present invention under different relative humidity changes song
Line chart；
Fig. 8 is that poly-D-lysine prepared by the present invention/multi-walled carbon nanotube composite membrane is real-time under different relative humidity
Resistance change curves figure.
Specific embodiment
In order to make the objectives, technical solutions, and advantages of the present invention clearer, with reference to the accompanying drawings and embodiments, right
The present invention is further elaborated.It should be appreciated that described herein, specific examples are only used to explain the present invention, not
For limiting the present invention, i.e., described embodiments are only a part of the embodiments of the present invention, instead of all the embodiments.
Therefore, the detailed description of the embodiment of the present invention provided in the accompanying drawings is not intended to limit below claimed
The scope of the present invention, but be merely representative of selected embodiment of the invention.Based on the embodiment of the present invention, those skilled in the art
Member's every other embodiment obtained without making creative work, shall fall within the protection scope of the present invention.
It should be noted that the relational terms of term " first " and " second " or the like be used merely to an entity or
Operation is distinguished with another entity or operation, and without necessarily requiring or implying between these entities or operation, there are any
This actual relationship or sequence.Moreover, the terms "include", "comprise" or its any other variant be intended to it is non-exclusive
Property include so that include a series of elements process, method, article or equipment not only include those elements, but also
Further include other elements that are not explicitly listed, or further include for this process, method, article or equipment it is intrinsic
Element.In the absence of more restrictions, the element limited by sentence "including a ...", it is not excluded that including described
There is also other identical elements in the process, method, article or equipment of element.
The problems such as in order to solve single carbon material humidity sensor difference in response and slow resume speed, to enhance single carbon system
The humidity sensitive performance of material humidity sensor, it is multiple that the present invention provides a kind of wet sensitive based on polylysine modification carbon-based material
The humidity sensor for closing film, including Sensitive Apparatus and the wet sensitive composite membrane that is arranged on Sensitive Apparatus, the wet sensitive composite membrane
Material is made by polylysine modification carbon-based material.The carbon-based material is single-walled carbon nanotube, multi-walled carbon nanotube, form
For the graphene of quantum dot, nanometer sheet, nanometer plate or nano wire, graphene oxide, redox graphene, carbon nano-fiber,
C60, graphite, nanoporous carbon and function dough one or more of carbon-based materials such as carbon material combination；The function
The carbon material of dough be amination graphene, hydroxylating graphene, carboxylated graphene, fluorinated graphene, dredge base graphite alkene,
Amination graphene oxide, carboxylated graphene oxide, Fluorinated graphene oxide, dredges baseization oxidation at hydroxylating graphene oxide
Graphene, reductive amination graphene oxide, hydroxylating redox graphene, carboxylated redox graphene, fluorination are also
The combination of one or more of the carbon-based materials such as former graphene oxide and thin base redox graphene；The Sensitive Apparatus
Interdigital electrode, one kind of quartz crystal microbalance (QCM) device for flexible or rigid substrate；The thickness of the wet sensitive composite membrane
It is 50nm-50 μm.The poly-D-lysine dispersion liquid and carbon-based material dispersion liquid by spraying, spin coating, drop coating, inkjet printing,
The techniques such as electrostatic spinning, electrochemical growth or self assembly prepare the wet sensitive composite membrane of single-layer or multi-layer on Sensitive Apparatus.
The preparation method of the humidity sensor of wet sensitive composite membrane based on polylysine modification carbon-based material, including it is following
Step:
1. being pre-processed to Sensitive Apparatus；
Step 1. in, the Sensitive Apparatus is the interdigital electrode of flexible or rigid substrate, quartz crystal microbalance (QCM) device
One kind of part, the pre-treatment step of the Sensitive Apparatus include: successively in deionized water, acetone, alcohol and to go Sensitive Apparatus
It cleans in ionized water, is then dried up with nitrogen.
2. preparing poly-D-lysine dispersion liquid, carbon-based material dispersion liquid is prepared；
Poly-D-lysine dispersion liquid are as follows: solvent is deionized water, the poly-D-lysine dispersion liquid of 0.01%w/v concentration；Institute
Stating carbon-based material is single-walled carbon nanotube, multi-walled carbon nanotube, the stone that form is quantum dot, nanometer sheet, nanometer plate or nano wire
The carbon materials of black alkene, graphene oxide, redox graphene, carbon nano-fiber, C60, graphite, nanoporous carbon and function dough
The combination of one or more of the carbon-based materials such as material；The carbon material of the function dough is amination graphene, hydroxyl fossil
Black alkene, carboxylated graphene, fluorinated graphene, dredge base graphite alkene, amination graphene oxide, hydroxylating graphene oxide,
Carboxylated graphene oxide, dredges base graphene oxide, reductive amination graphene oxide, hydroxylating at Fluorinated graphene oxide
Redox graphene, carboxylated redox graphene, fluorination redox graphene and thin base redox graphene
The combination of one or more of equal carbon-based materials.
3. 2. poly-D-lysine dispersion liquid and carbon-based material dispersion liquid that step is prepared pass through spraying, spin coating, drop coating, spray
The wet sensitive that the techniques such as black printing, electrostatic spinning, electrochemical growth or self assembly prepare single-layer or multi-layer on Sensitive Apparatus is compound
Film；
4. being finally dried to obtain the humidity sensor of the wet sensitive composite membrane based on polylysine modification carbon-based material；
The condition of the drying are as follows: 12 hours dry under 60 DEG C of environment.
Feature and performance of the invention are described in further detail with reference to embodiments.
Embodiment 1
The Sensitive Apparatus that the present embodiment is selected is interdigital electrode, and the interdigital electrode selection is produced on flexible PI substrate golden
Electrode, the interdigital spacing of the interdigital electrode are 200 μm, and the interdigital width of the interdigital electrode is 200 μm, the interdigital electrode
Thickness of electrode be 100nm；The carbon-based material selected in the present embodiment is multi-walled carbon nanotube, specific process step are as follows:
(1) the flexible interdigital electrode for preparing PI substrate cuts flexible PI substrate using cutter, cuts specification and is
15×15mm；PI substrate after reduction is put in substrate frame successively in dish washing liquid, deionized water, acetone, alcohol and deionization
It is cleaned in water, then each cleaning process ultrasound 15-30 minutes is dried up with nitrogen；The interdigital electricity of gold is deposited in PI substrate
Pole；
(2) poly-D-lysine dispersion liquid is prepared, solvent is deionized water, configures the poly-D-lysine of 0.01%w/v concentration
Dispersion liquid；The dispersion liquid of multi-walled carbon nanotube is prepared, the concentration for measuring doses at room temperature is that 2wt% multi wall carbon is received
Mitron dispersion liquid, it is spare after ultrasonic treatment after diluting 200 times with deionized water；
(3) the poly-D-lysine dispersion liquid in step (2) is carried out with multi-walled carbon nanotube solution according to the volume ratio of 1:1
Mixing, and it is aided with stirring and ultrasonic treatment forms uniform mixed solution；By the mixing of poly-D-lysine and multi-walled carbon nanotube
Solution prepares composite sensitive film in the interdigital electrode of flexible PI substrate by drop coating technique；
(4) 12 hours dry under 60 DEG C of environment, it is multiple to obtain the wet sensitive based on polylysine modification multi-walled carbon nanotube
Close the humidity sensor of film.
Embodiment 2
The Sensitive Apparatus that the present embodiment is selected is interdigital electrode, and the interdigital electrode selects the silver electrode of silicon base, described
The interdigital spacing of interdigital electrode is 50 μm, and the interdigital width of the interdigital electrode is 50 μm, the thickness of electrode of the interdigital electrode
For 50nm；The carbon-based material selected in the present embodiment is graphene, specific process step are as follows:
(1) silicon base interdigital electrode is successively cleaned in deionized water, acetone, alcohol and deionized water, then uses nitrogen
Gas is dried up；
(2) poly-D-lysine dispersion liquid is prepared, solvent is deionized water, configures the poly-D-lysine of 0.01%w/v concentration
Dispersion liquid；The dispersion liquid of graphene is prepared, the concentration for measuring doses at room temperature is the graphene dispersion of 2mg/ml
Liquid, it is spare after ultrasonic treatment after diluting 200 times with deionized water；
(3) it by the poly-D-lysine dispersion liquid and graphene dispersing solution in step (2), by spraying process, is first pitched in silver
Refer to and deposit graphene film on electrode, after 2 hours dry, poly-D-lysine film is then deposited on graphene film；
(4) 12 hours dry under 60 DEG C of environment, obtain the wet sensitive composite membrane based on polylysine modification graphene
Humidity sensor.
Embodiment 3
The Sensitive Apparatus that the present embodiment is selected is quartz crystal microbalance (QCM) device, the quartz crystal microbalance
(QCM) metal electrode is silver electrode, base frequency 9.98MHz up and down for device selection；The carbon system selected in the present embodiment
Material is graphene oxide, specific process step are as follows:
(1) quartz crystal microbalance (QCM) device is successively cleaned in deionized water, acetone, alcohol and deionized water,
Then it is dried up with nitrogen；
(2) poly-D-lysine dispersion liquid is prepared, solvent is deionized water, configures the poly-D-lysine of 0.01%w/v concentration
Dispersion liquid；Graphene oxide dispersion is prepared, the graphene oxide dispersion of doses is measured at room temperature, is diluted to
Concentration is 0.2mg/ml, spare after ultrasonic treatment；
(3) the poly-D-lysine dispersion liquid and graphene oxide dispersion in step (2) are first existed by spraying process
The two sides of metal electrode up and down of quartz crystal microbalance (QCM) device deposits poly-D-lysine film respectively, after 2 hours dry,
Then redeposited graphene oxide film, forms composite sensing film；
(4) 12 hours dry under 60 DEG C of environment, it is compound to obtain the wet sensitive based on polylysine modification graphene oxide
The humidity sensor of film.
Embodiment 4
The Sensitive Apparatus that the present embodiment is selected is quartz crystal microbalance (QCM) device, the quartz crystal microbalance
(QCM) metal electrode is gold electrode, base frequency 9.98MHz up and down for device selection；The carbon system selected in the present embodiment
Material is redox graphene, specific process step are as follows:
(1) quartz crystal microbalance (QCM) device is successively cleaned in deionized water, acetone, alcohol and deionized water,
Then it is dried up with nitrogen；
(2) poly-D-lysine dispersion liquid is prepared, solvent is deionized water, configures the poly-D-lysine of 0.01%w/v concentration
Dispersion liquid；Redox graphene dispersion liquid is prepared, measures the redox graphene dispersion of doses at room temperature
Liquid, being diluted to concentration is 0.5mg/ml, spare after ultrasonic treatment；
(3) by the poly-D-lysine dispersion liquid and redox graphene dispersion liquid in step (2), by spraying process,
First oxidation graphene film is deposited respectively on the upper/lower electrode two sides of quartz crystal microbalance (QCM) device, it is 2 hours dry
Afterwards, redeposited poly-D-lysine film forms composite sensing film；
(4) 12 hours dry under 60 DEG C of environment, it is compound to obtain the wet sensitive based on polylysine modification graphene oxide
The humidity sensor of film.
Comparative example 1
The Sensitive Apparatus that the present embodiment is selected is interdigital electrode, and the interdigital electrode selection is produced on flexible PI substrate golden
Electrode, the interdigital spacing of the interdigital electrode are 200 μm, and the interdigital width of the interdigital electrode is 200 μm, the interdigital electrode
Thickness of electrode be 100nm；The carbon-based material selected in the present embodiment is multi-walled carbon nanotube, specific process step are as follows:
(1) the flexible interdigital electrode for preparing PI substrate cuts flexible PI substrate using cutter, cuts specification and is
15×15mm；PI substrate after reduction is put in substrate frame successively in dish washing liquid, deionized water, acetone, alcohol and deionization
It is cleaned in water, then each cleaning process ultrasound 15-30 minutes is dried up with nitrogen；The interdigital electricity of gold is deposited in PI substrate
Pole；
(2) dispersion liquid of multi-walled carbon nanotube is prepared, the concentration for measuring doses at room temperature is 2wt% multi wall
Carbon nano tube dispersion liquid, it is spare after ultrasonic treatment after diluting 200 times with deionized water；
(3) the multi-walled carbon nanotube solution in step (2) is passed through into drop coating technique in the interdigital electrode of flexible PI substrate
Prepare composite sensitive film；
(4) 12 hours dry under 60 DEG C of environment, it is multiple to obtain the wet sensitive based on polylysine modification multi-walled carbon nanotube
Close the humidity sensor of film.
Fig. 1 is the schematic arrangement of poly-D-lysine, and as can be seen from the figure poly-D-lysine theoretically has ammonia
Base, imino group and carbon-based equal hydrophilic functional groups.
Fig. 2 is field emission scanning electron microscope (FE-SEM) figure of the film of pure multi-walled carbon nanotube, and Fig. 3 is of the present invention
Poly-D-lysine/multi-walled carbon nanotube composite membrane field emission scanning electron microscope (FE-SEM) figure, from figure 2 it can be seen that pure more
Wall carbon nano-tube film is formed by smooth carbon nanotube, and poly occurs in poly-D-lysine/multi-walled carbon nanotube composite membrane
Lysine coats the phenomenon that multi-walled carbon nanotube.
Fig. 4 is X-ray photoelectron spectroscopic analysis (XPS) analysis chart of pure multi-wall carbon nano-tube film in C1s, and Fig. 5 is this
Invent X-ray photoelectron spectroscopic analysis (XPS) figure of the poly-D-lysine/multi-walled carbon nanotube composite membrane being related on C1s, figure
6 be X-ray photoelectron spectroscopic analysis (XPS) of the poly-D-lysine of the present invention/multi-walled carbon nanotube composite membrane on N1s
Figure, as seen from Figure 4, the combination at 284.6,285.0 and 286.5eV can respectively correspond C-C, C-H and C-O key.With
Pure multi-walled carbon nanotube is compared, the peak C-N and C-O/C=O that the laminated film in Fig. 5 occurs near 285.7 and 286.7eV,
Show the presence of poly-D-lysine in poly-D-lysine/multi-walled carbon nanotube laminated film.In Fig. 6, N1s is in 400.2 Hes
Combination at 401.8eV can correspond respectively to have hydrophilic amino (imino group) group (- NH2/-NH) and quaternary ammonium or proton
Change nitrogen (- C-N+/-NH2H+).XPS analysis result further confirms that poly-D-lysine has hydrophilic functional group abundant.
Fig. 7 is that a kind of real time resistance of the pure multi-wall carbon nano-tube periosteum prepared by the present invention under different relative humidity changes song
Line chart, Fig. 8 are poly-D-lysine prepared by the present invention/real time resistance of the multi-walled carbon nanotube composite membrane under different relative humidity
Change curve.The resistance for being observed that wet sensitive of two humidity sensors in 0-91.5%RH responds from Fig. 7 and Fig. 8 becomes
Change shows a positive humidity coefficient.Compared with poly-D-lysine/multi-walled carbon nanotube composite membrane humidity sensor, pure multi wall carbon
The response of nanotube humidity sensor is low, restores slow.Poly-D-lysine/multi-walled carbon nanotube composite membrane humidity sensor sound
600 times should be higher than at 91.5%RH than pure multi-walled carbon nanotube humidity sensor, this shows that the addition of poly-D-lysine is very big
Ground improves the wet sensitive response of pure multi-walled carbon nanotube.In addition, poly-D-lysine/multi-walled carbon nanotube composite membrane humidity sensor
Response the excellent linearity (R is shown under 5.2% to 23.8%RH range2=0.9990), response 60.8% to
Significant increase in the range of 91.5%RH, therefore the switching characteristic under high humidity state can be used for detecting high humidity environment.
The foregoing is merely illustrative of the preferred embodiments of the present invention, is not intended to limit the invention, all in essence of the invention
Made any modifications, equivalent replacements, and improvements etc., should all be included in the protection scope of the present invention within mind and principle.
Claims (10)
1. the humidity sensor of the wet sensitive composite membrane based on polylysine modification carbon-based material, it is characterised in that: including sensitivity
Device and the wet sensitive composite membrane being arranged on Sensitive Apparatus, the material of the wet sensitive composite membrane is by polylysine modification carbon system material
Material is made.
2. the humidity sensor of the wet sensitive composite membrane based on polylysine modification carbon-based material as described in claim 1,
Be characterized in that: the carbon-based material is single-walled carbon nanotube, multi-walled carbon nanotube, form be quantum dot, nanometer sheet, nanometer plate or
Graphene, graphene oxide, redox graphene, carbon nano-fiber, C60, graphite, nanoporous carbon and the function of nano wire
The combination of one or more of the carbon material of dough.
3. the humidity sensor of the wet sensitive composite membrane based on polylysine modification carbon-based material as claimed in claim 2,
Be characterized in that: the carbon material of the function dough is amination graphene, hydroxylating graphene, carboxylated graphene, fluorination stone
Black alkene dredges base graphite alkene, amination graphene oxide, hydroxylating graphene oxide, carboxylated graphene oxide, fluorinated
Graphene dredges base graphene oxide, reductive amination graphene oxide, hydroxylating redox graphene, carboxylated reduction
The combination of one or more of graphene oxide, fluorination redox graphene and thin base redox graphene.
4. the humidity sensor of the wet sensitive composite membrane based on polylysine modification carbon-based material as described in claim 1,
Be characterized in that: the Sensitive Apparatus is the flexible or rigid interdigital electrode of substrate and one kind of quartz crystal microbalance device.
5. the humidity sensor of the wet sensitive composite membrane based on polylysine modification carbon-based material as described in claim 1,
Be characterized in that: the wet sensitive composite membrane with a thickness of 50nm-50 μm.
6. the preparation method of the humidity sensor of the wet sensitive composite membrane based on polylysine modification carbon-based material, feature exist
In, comprising the following steps:
1. being pre-processed to Sensitive Apparatus；
2. preparing poly-D-lysine dispersion liquid, carbon-based material dispersion liquid is prepared；
3. 2. poly-D-lysine dispersion liquid and carbon-based material dispersion liquid that step is prepared is beaten by spraying, spin coating, drop coating, ink-jet
The techniques such as print, electrostatic spinning, electrochemical growth or self assembly prepare the wet sensitive composite membrane of single-layer or multi-layer on Sensitive Apparatus；
4. being finally dried to obtain the humidity sensor of the wet sensitive composite membrane based on polylysine modification carbon-based material.
7. the system of the humidity sensor of the wet sensitive composite membrane based on polylysine modification carbon-based material as claimed in claim 6
Preparation Method, it is characterised in that: step 1. in, the Sensitive Apparatus is that the interdigital electrode of flexible or rigid substrate, quartz crystal are micro-
One kind of balance device, the pre-treatment step of the Sensitive Apparatus include: by Sensitive Apparatus successively in deionized water, acetone, wine
It cleans in essence and deionized water, is then dried up with nitrogen.
8. the system of the humidity sensor of the wet sensitive composite membrane based on polylysine modification carbon-based material as claimed in claim 6
Preparation Method, it is characterised in that: step 2. in, poly-D-lysine dispersion liquid are as follows: solvent is the 0.01%w/v concentration of deionized water
Poly-D-lysine dispersion liquid.
9. the system of the humidity sensor of the wet sensitive composite membrane based on polylysine modification carbon-based material as claimed in claim 6
Preparation Method, it is characterised in that: step 2. in, the carbon-based material is single-walled carbon nanotube, multi-walled carbon nanotube, form are quantum
Point, nanometer sheet, nanometer plate or nano wire graphene, graphene oxide, redox graphene, carbon nano-fiber, C60, stone
The combination of one or more of the carbon material of ink, nanoporous carbon and function dough.
10. the humidity sensor of the wet sensitive composite membrane based on polylysine modification carbon-based material as claimed in claim 9
Preparation method, it is characterised in that: the carbon material of the function dough is amination graphene, hydroxylating graphene, carboxyl fossil
Black alkene, dredges base graphite alkene, amination graphene oxide, hydroxylating graphene oxide, carboxylated graphite oxide at fluorinated graphene
Alkene, Fluorinated graphene oxide, dredge base graphene oxide, reductive amination graphene oxide, hydroxylating redox graphene,
One or more of carboxylated redox graphene, fluorination redox graphene and thin base redox graphene
Combination.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110726757A (en) * | 2019-10-17 | 2020-01-24 | 电子科技大学 | Humidity sensor based on halloysite nanotube and preparation method thereof |
| CN112763551A (en) * | 2020-12-29 | 2021-05-07 | 电子科技大学 | Nitrogen dioxide sensor based on composite material blocking effect and preparation method thereof |
| CN112763559A (en) * | 2020-12-29 | 2021-05-07 | 电子科技大学 | Gamma-polyglutamic acid based humidity sensor and preparation method thereof |
| CN112798659A (en) * | 2020-12-29 | 2021-05-14 | 电子科技大学 | Humidity sensor based on sepiolite modified carbon material and preparation method thereof |
| CN112924492A (en) * | 2021-03-18 | 2021-06-08 | 电子科技大学 | Self-powered humidity sensor based on composite spinning film and preparation method thereof |
| EP3992622A1 (en) * | 2020-11-03 | 2022-05-04 | Institutul National de Cercetare-Dezvoltare Pentru Microtehnolgie - IMT Bucuresti INCD | Quaternary hydrophilic nanohybrid composition for resistive humidity sensors |
Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101003194A (en) * | 2006-01-19 | 2007-07-25 | 中国科学院化学研究所 | Humidity sensitive composite membrane of polymer, preparation method and application |
| WO2007126051A1 (en) * | 2006-04-28 | 2007-11-08 | Fujirebio Inc. | Reagent for assaying antiphospholipid antibody |
| WO2012042459A1 (en) * | 2010-09-27 | 2012-04-05 | Scuola Superiore Di Studi Universitari E Di Perfezionamento Sant'anna | Magnetised stem cells and use thereof |
| CN102725629A (en) * | 2009-10-01 | 2012-10-10 | 美敦力迷你迈德公司 | Analyte sensor apparatuses having interference rejection membranes and methods for making and using them |
| CN102866181A (en) * | 2012-09-30 | 2013-01-09 | 浙江大学 | Polyaniline/ titanium dioxide nanometer composite impedance type thin film gas sensor and preparation method thereof |
| CN102890110A (en) * | 2011-07-22 | 2013-01-23 | 拜尔健康护理有限责任公司 | Biosensor desiccant system having enhanced measurement performance |
| CN103901089A (en) * | 2014-04-16 | 2014-07-02 | 国家纳米科学中心 | Sensor for detecting nerve cell electrophysiology signal and manufacturing method and detection method of sensor |
| CN106871775A (en) * | 2017-02-13 | 2017-06-20 | 电子科技大学 | Carbon-based material high molecular polymer strain sensitive film and preparation method |
| CN107014879A (en) * | 2017-04-12 | 2017-08-04 | 西北师范大学 | A kind of preparation and application of chiral Recognition material modified electrode |
| CN108066805A (en) * | 2016-11-17 | 2018-05-25 | 中国科学院大连化学物理研究所 | A kind of bionical bacteriostatic film of epsilon-polylysine and its preparation and application |
-
2019
- 2019-01-11 CN CN201910026467.6A patent/CN109613071B/en active Active
Patent Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101003194A (en) * | 2006-01-19 | 2007-07-25 | 中国科学院化学研究所 | Humidity sensitive composite membrane of polymer, preparation method and application |
| WO2007126051A1 (en) * | 2006-04-28 | 2007-11-08 | Fujirebio Inc. | Reagent for assaying antiphospholipid antibody |
| CN102725629A (en) * | 2009-10-01 | 2012-10-10 | 美敦力迷你迈德公司 | Analyte sensor apparatuses having interference rejection membranes and methods for making and using them |
| WO2012042459A1 (en) * | 2010-09-27 | 2012-04-05 | Scuola Superiore Di Studi Universitari E Di Perfezionamento Sant'anna | Magnetised stem cells and use thereof |
| CN102890110A (en) * | 2011-07-22 | 2013-01-23 | 拜尔健康护理有限责任公司 | Biosensor desiccant system having enhanced measurement performance |
| CN102866181A (en) * | 2012-09-30 | 2013-01-09 | 浙江大学 | Polyaniline/ titanium dioxide nanometer composite impedance type thin film gas sensor and preparation method thereof |
| CN103901089A (en) * | 2014-04-16 | 2014-07-02 | 国家纳米科学中心 | Sensor for detecting nerve cell electrophysiology signal and manufacturing method and detection method of sensor |
| CN108066805A (en) * | 2016-11-17 | 2018-05-25 | 中国科学院大连化学物理研究所 | A kind of bionical bacteriostatic film of epsilon-polylysine and its preparation and application |
| CN106871775A (en) * | 2017-02-13 | 2017-06-20 | 电子科技大学 | Carbon-based material high molecular polymer strain sensitive film and preparation method |
| CN107014879A (en) * | 2017-04-12 | 2017-08-04 | 西北师范大学 | A kind of preparation and application of chiral Recognition material modified electrode |
Non-Patent Citations (3)
| Title |
|---|
| KUM-PYO YOOA ET AL: "Novel resistive-type humidity sensor based on multiwall carbon nanotube/polyimide composite films", 《SENSORS AND ACTUATORS B: CHEMICAL》 * |
| SURAJIT SOME ET AL: "Dual Functions of Highly Potent Graphene Derivative Poly‑L‑Lysine Composites To Inhibit Bacteria and Support Human Cells", 《ACS NANO》 * |
| 程亚玮等: "碳纳米管基聚合物水凝胶研究进展", 《中国科技论文》 * |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110726757A (en) * | 2019-10-17 | 2020-01-24 | 电子科技大学 | Humidity sensor based on halloysite nanotube and preparation method thereof |
| CN110726757B (en) * | 2019-10-17 | 2021-12-03 | 电子科技大学 | Humidity sensor based on halloysite nanotube and preparation method thereof |
| EP3992622A1 (en) * | 2020-11-03 | 2022-05-04 | Institutul National de Cercetare-Dezvoltare Pentru Microtehnolgie - IMT Bucuresti INCD | Quaternary hydrophilic nanohybrid composition for resistive humidity sensors |
| CN112763551A (en) * | 2020-12-29 | 2021-05-07 | 电子科技大学 | Nitrogen dioxide sensor based on composite material blocking effect and preparation method thereof |
| CN112763559A (en) * | 2020-12-29 | 2021-05-07 | 电子科技大学 | Gamma-polyglutamic acid based humidity sensor and preparation method thereof |
| CN112798659A (en) * | 2020-12-29 | 2021-05-14 | 电子科技大学 | Humidity sensor based on sepiolite modified carbon material and preparation method thereof |
| CN112763559B (en) * | 2020-12-29 | 2022-03-18 | 电子科技大学 | Gamma-polyglutamic acid based humidity sensor and preparation method thereof |
| CN112924492A (en) * | 2021-03-18 | 2021-06-08 | 电子科技大学 | Self-powered humidity sensor based on composite spinning film and preparation method thereof |
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