CN109870482A - A kind of gas sensor and preparation method thereof - Google Patents
A kind of gas sensor and preparation method thereof Download PDFInfo
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- CN109870482A CN109870482A CN201910206689.6A CN201910206689A CN109870482A CN 109870482 A CN109870482 A CN 109870482A CN 201910206689 A CN201910206689 A CN 201910206689A CN 109870482 A CN109870482 A CN 109870482A
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Abstract
The invention discloses a kind of gas sensors and preparation method thereof, for improving the gas-sensitive property of gas sensor, to improve the sensitivity of gas sensor.The production method of gas sensor therein includes: to make the gas sensing material with multiple hole configurationss by Kynoar PVDF and polyaniline PAN；First electrode and second electrode and gas sensing layer are formed on insulating substrate, wherein the first electrode and the second electrode are located at the opposite end of the same side of the gas sensing layer, and the gas sensing layer is formed by the gas sensing material.
Description
Technical field
The present invention relates to sensor technical field, in particular to a kind of gas sensor and preparation method thereof.
Background technique
Gas sensor is the sensor for detection gas concentration and ingredient, it is for environmental protection and safety supervision side
Face plays epochmaking effect.
When gas sensor in gas sensor incudes gas, gas is contacted with gas sensor, and is adsorbed or flowed in gas
On quick element, so that the electrical characteristics of gas sensor change, to detect gas.
But the structure of the gas sensor in current gas sensor is more compact, the surface of only gas sensor can
To incude gas, so the electrical characteristics of gas sensor change, amplitude is smaller, i.e. the sensitivity of gas sensor is lower.
Summary of the invention
The embodiment of the present application provides a kind of gas sensor and preparation method thereof, and the air-sensitive for improving gas sensor is special
Property, to improve the sensitivity of gas sensor.
In a first aspect, the embodiment of the present application provides a kind of production method of gas sensor, this method comprises:
By Kynoar PVDF and polyaniline PAN, the gas sensing material with multiple hole configurationss is made；
First electrode and second electrode and gas sensing layer are formed on insulating substrate, wherein the first electrode and
The second electrode is located at the opposite end of the same side of the gas sensing layer, and the gas sensing layer is by the gas sensing
Material is formed.
The embodiment of the present application provides a kind of new material, for making in gas sensor for incuding the gas of gas
Inductive layer.This new material can be made up of Kynoar and polyaniline, and polyaniline is for incuding gas, polyvinylidene fluoride
Alkene can be used for expanding the area of polyaniline induction gas.For example, Kynoar is made for the structure with multiple holes,
Polyaniline is free in hole in this way, and when incuding gas, the contact area with gas is the surface area of polyaniline molecule, that is,
The internal surface area of multiple holes for the surface contacted compared to polyaniline with gas, increases the surface area of induction gas, from
And the electrical characteristics for increasing gas sensor change amplitude, improve the sensitivity of gas sensor.
In a kind of possible embodiment, by Kynoar PVDF and polyaniline PAN, production has multiple holes
The gas sensing material of structure, comprising:
PVDF is dissolved using the first solvent, so that the PVDF has multiple holes；
PAN is adulterated in the PVDF with multiple hole configurationss, forms the gas sensing material.
In the embodiment of the present application, Kynoar first can be dissolved using solvent when making gas sensing material, will gathered
Vinylidene becomes hole configurations from spherulitic crystal structure, then in Kynoar upon dissolution filling doping for incuding gas
Polyaniline.
In a kind of possible embodiment, the proportion of first solvent and the PVDF are 50:1~150:1.
The different ratio of solvent and Kynoar, the sensitivity of obtained gas sensing material perception gas is not yet
Together.In the embodiment of the present invention, it is preferable that the proportion of solvent and Kynoar is located at 50:1~150:1, with what is guaranteed as far as possible
The sensitivity of gas sensing material perception gas.
In a kind of possible embodiment, first electrode and second electrode and gas sense are formed on insulating substrate
Answer layer, comprising:
The gas sensing material is coated on the insulating substrate using spin coating mode, forms the gas sensing
Layer；
The first electrode and described is formed far from the opposite end of the insulating substrate side in the gas sensing layer
Second electrode.
In a kind of possible embodiment, first electrode and second electrode and gas sense are formed on insulating substrate
Answer layer, comprising:
Opposite end on the insulating substrate forms the first electrode and the second electrode；
Layer where the gas sensing material is coated in the first electrode and the second electrode using spin coating mode
It is upper to form the gas sensing layer.
In the embodiment of the present invention, when making gas sensor, gas sensing can be placed on first electrode and second
Under electrode, gas sensing can also be placed in first electrode and second electrode, the embodiment of the present invention is to first electrode and
The relative positional relationship of two electrodes and gas sensing layer is with no restriction.
In a kind of possible embodiment, further includes:
The gas sensor is placed in acidic liquid, is detected with the sensitivity to the gas sensor；
Remove the acid solution that the gas sensor carries.
Since gas and gas sensing layer react, acid ion can be generated, so that there is hole on polyaniline chain,
Electron cloud redistribution, makes polyaniline that high conductivity be presented.The electric conductivity of polyaniline is higher, and the sensitivity of gas sensing layer is got over
Height, so, the embodiment of the present application can detect the sensitivity of gas sensor when making gas sensor with acid solution,
To guarantee the sensitivity of gas sensor as far as possible.
In a kind of possible embodiment, the pH value of the acid solution is located in [0.8,1.2] range.
In the embodiment of the present application, the pH value of the acid solution of use is located in [0.8,1.2] range, available preferable
The doping effect of acid ion.
In a first aspect, the embodiment of the present application provides a kind of gas sensor, which includes:
Insulating substrate；
Gas sensing layer is arranged on the insulating substrate, wherein the gas sensing layer is by with multiple hole configurationss
Gas sensing material formed, the gas sensing material be PVDF and PAN polymer；
First electrode and second electrode, the first electrode and the second electrode are located at the same of the gas sensing layer
The opposite end of side.
In a kind of possible embodiment, it is remote that the first electrode and the second electrode are located at the gas sensing layer
Side from the insulating substrate；Or,
The first electrode and the second electrode are located at the gas sensing layer close to the side of the insulating substrate.
In a kind of possible embodiment, the insulating substrate is flexible insulating substrate.
Detailed description of the invention
Fig. 1 is the flow diagram of the production method of gas sensor provided by the embodiments of the present application；
Fig. 2 is a kind of structural schematic diagram of the Kynoar of the prior art；
Fig. 3 is a kind of structural schematic diagram of Kynoar provided by the embodiments of the present application；
Fig. 4 is the Kynoar of the prior art and the polymerization schematic diagram of polyaniline；
Fig. 5 is the polymerization schematic diagram of Kynoar provided by the embodiments of the present application and polyaniline；
Fig. 6 is a kind of structural schematic diagram of gas sensor provided by the embodiments of the present application；
Fig. 7 is a kind of structural schematic diagram of gas sensor provided by the embodiments of the present application；
Fig. 8 is a kind of schematic diagram that gas sensor provided by the embodiments of the present application incudes gas；
Fig. 9 is a kind of schematic diagram that gas sensor provided by the embodiments of the present application incudes gas.
Specific embodiment
Understand to make the objectives, technical solutions, and advantages of the present invention clearer, below in conjunction with the embodiment of the present application
In attached drawing, the technical scheme in the embodiment of the application is clearly and completely described.
The structure of gas sensor in current gas sensor is more compact, and only the surface of gas sensor can incude
Gas, so the electrical characteristics of gas sensor change, amplitude is smaller, i.e. the sensitivity of gas sensor is lower.
In consideration of it, the embodiment of the present application provides a kind of material of new production gas sensor, which can be
The polymer of PVDF and PAN, and have multiple hole configurationss, PAN is located in hole configurations, so that PAN and gas connect
Contacting surface product increases, and improves the sensitivity of gas sensor.
With reference to the accompanying drawing, to the specific embodiment of gas sensor provided by the embodiments of the present application and preparation method thereof
It is described in detail.The thickness of each film layer and shape do not reflect actual proportions in attached drawing, and purpose is the schematically illustrate present invention
Content.
Referring to Figure 1, the embodiment of the present application provides a kind of production method of gas sensor, the detailed process of this method
It is described as follows:
S101, pass through Kynoar and polyaniline, gas sensing material of the production with multiple hole configurationss；
S102, first electrode and second electrode and gas sensing layer are formed on insulating substrate, wherein first electrode
It is located at the opposite end of the same side of gas sensing layer with second electrode, gas sensing layer is formed by gas sensing material.
For the embodiment of the present application when making gas sensor, production forms the gas sensing layer for incuding gas first
Making material, i.e. gas sensing material.The embodiment of the present application uses the polyaniline PAN with electrical properties to incude gas.Due to
Electric conductivity is presented in PAN after acid doping, so gas reacts with PAN when PAN and gas contact, forms sour example, mixes
It is miscellaneous in the pan, to detect the electric conductivity of PAN, according to the corresponding relationship of electric conductivity and gas, the final detection for realizing gas.
The contact area of gas and PAN are bigger, and the amplitude that the conductive characteristic of PAN changes is bigger, that is, PAN incudes gas
Sensitivity it is higher.The embodiment of the present application has made a kind of new gas sense to improve the sensitivity that PAN incudes gas first
Material is answered, which includes Kynoar PVDF and PAN, and has multiple hole configurationss.For example, PVDF has
Multiple hole configurationss, hole configurations of the PAN molecular dopant in PVDF.When this gas sensing material and gas contact, gas
The surface of PAN molecule is adsorbed, then the contact area of gas and PAN are actually the internal surface area in hole, only compared to gas
It is the surface foundation with PAN, it is clear that gas sensing material provided by the embodiments of the present application can increase the area of gas absorption,
To improve the sensitivity of induction gas.
Specifically, the embodiment of the present application first makes the PVDF with hole configurations.Firstly, referring to Fig. 2, Fig. 2 is PVDF
A kind of structural schematic diagram, from figure 2 it can be seen that PVDF itself is a kind of structure of spherocrystal configuration.
Spherulitic crystal structure is destroyed, or the interval between spherulitic crystal structure is expanded, so that it may obtain multiple hole configurationss, example
Such as, in a kind of possible embodiment, the embodiment of the present application can dissolve PVDF using the first solvent, so that PVDF is with more
A hole.It should be noted that the first solvent can be solvent miscible with water, first solvent itself is not change with PVDF
Reaction is learned, for example, the first solvent can be dinethylformamide.Dissolved PVDF has multiple hole configurationss, such as Fig. 3
It is shown.
When first solvent is different with the proportion of PVDF, the degree for dissolving PVDF is also different, then the quantity of hole
Different, the sensitivity of finally obtained gas sensing material induction gas is also different.In a kind of possible embodiment party
In formula, the proportion of the first solvent and PVDF are 50:1~150:1, improve the dissolution degree of PVDF as far as possible, obtain more hole,
With the sensitivity of the gas sensing material perception gas guaranteed as far as possible.
It obtains after there is the PVDF of hole configurations, PAN can be entrained in the PVDF with hole configurations.Due to having
The PVDF of hole configurations makes the particle of PVDF smaller, and the PAN molecule of absorption is more.For example, Fig. 4 is referred to, for no hole
The schematic diagram of the PVDF doping PAN of structure, and Fig. 5 is referred to, the schematic diagram of PAN is adulterated for the PVDF with hole configurations.
The circle signal PVDF being relatively large in diameter in Fig. 4 and Fig. 5, the lesser circle of diameter only have PAN molecule, and comparison diagram 4 and Fig. 5 are it is found that have
The PAN molecule of the PVDF absorption of hole configurations is more, thus the gas sense formed using the PVDF doping PAN with hole configurations
Material is answered, since PAN molecule is more, the sensitivity for incuding gas is also higher.
After obtaining gas sensing material, gas sensor can be started from.Specifically, Fig. 6 is referred to, is a kind of gas
The structural schematic diagram of dependent sensor.Substrate 10 can be provided first, which can be flexible substrates, soft so as to make
Property gas sensor.For example, flexible substrates can be using with preferable flexible PVDF.It on the substrate 10 successively can be with shape
At grid 101 and gate insulating layer 20, to obtain insulating substrate.First electrode 301 and the are formed on insulating substrate again
Two electrodes 302 and gas sensing layer 30, first electrode 301 here can be source electrode, and second electrode 302 can be drain electrode.
Gas sensing layer 30 is made of gas sensing material, since gas sensing material is the polymer of PVDF and PAN, and PVDF
Flexibility is higher, so the flexibility of gas sensing layer 30 is also higher, flexible gas sensor can be made.
Continuing with referring to Fig. 6, in a kind of possible embodiment, the embodiment of the present application can first be made on insulating substrate
Make gas sensing layer 30, then the both ends production first electrode 301 and second electrode 302 opposite in gas sensing layer 30.
For example, since gas sensing material is dissolved colloidal state, it is possible to be coated gas sensing material using spin coating mode
On insulating substrate, to form gas sensing layer 30.Again in opposite end of the gas sensing layer 30 far from insulating substrate side
Form first electrode 301 and second electrode 302.
Alternatively, referring to Fig. 7, in a kind of possible embodiment, the embodiment of the present application can be first on insulating substrate
First electrode and second electrode are made, then makes gas sensing layer.
For example, the opposite end on insulating substrate forms first electrode 301 and second electrode 302, then use spin coating side
Gas sensing material is coated on 302 place layer of first electrode 301 and second electrode and forms gas sensing layer 30 by formula.
Since the first solvent of the solvent PVDF in gas sensing material can evaporate, so will not influence made
Gas sensing layer 30.After making gas sensor, need to detect gas sensor, to obtain with higher sensitivity gas
Dependent sensor.Before the detection to gas sensor is introduced, the working principle of lower gas sensing layer 30 is first introduced below.
The electric conductivity of polyaniline depends not only on the degree of oxidation of main chain, and related with the doping level of Bronsted acid.
The doping of polyaniline is mainly controlled by diffusion process by spreading and chemically reacting two process control, doping initial stage.Average molecular
The lesser inorganic acid of quality is easy to spread, so doping effect is preferable.The biggish organic acid diffusion velocity of relative molecular mass compared with
Slow and influence factor is more.It when with protonic acid doping, preferentially protonates, generates charged in the imine nitrogen atom of strand
First excitation state polaron makes occur hole on polyaniline chain in doping valence band, i.e. p-type is adulterated, and so that intramolecular quinone ring is disappeared, electronics
Cloud redistributes, and positive charge delocalization makes polyaniline show high conductivity into big conjugatedπbond on N atom.
This is because the electroactive P electron conjugated structure in strand of polyaniline.With P electron system in strand
Expansion, P bonding state and P* antibonding state be respectively formed valence band and conduction band, and this non-localized P electron conjugated structure is doped can
Form p-type and N-type conductive state.The doping machine of cation vacancy is generated under oxidant effect different from other conducting polymers
System, number of electrons does not change during the doping of polyaniline, but the Bronsted acid by adulterating decompose generate H+ and to yin from
Sub (such as Cl-, sulfate radical, phosphate radical) enters main chain, formed with N atom in amine and imine group ining conjunction with extremely sub and dipole from
Domain is into the P key of entire strand, to make polyaniline that higher electric conductivity be presented.This unique mechanism of doping effect makes polyphenyl
The doping of amine and dedoping completely reversibility, doping level are influenced by factors such as pH value and current potentials, therefore polyaniline also has electrification
Learn activity change characteristic.
Gas sensor can be placed in acidic liquid by the embodiment of the present application when detecting to gas sensor,
It is detected with the sensitivity to gas sensor, removes the acid solution of gas sensor carrying after detection again, so as to
To filter out with higher sensitivity gas sensor.
Gas sensor impregnates in an acidic solution, with the growth of soaking time, is doped to the matter of gas sensing layer 30
Also institute is different for the amount of sub- acid, and the electric conductivity that gas sensing layer is presented also changes.The embodiment of the present application can acquire gas sense
The electric conductivity for answering layer 30 to be presented, according to the relationship of Bronsted acid amount and electric conductivity, to be inferred to the sensitivity of gas sensor.
In a kind of possible embodiment, analysis decision can be carried out to Bronsted acid amount and electric conductivity by the method for machine learning,
To realize the detection to gas sensor.
Certainly, gas sensor incudes gas, reacts to form Bronsted acid, so, the embodiment of the present application can also be straight
It connects and the gas sensor of production is placed in gaseous environment, and the electric conductivity of gas sensor is detected, thus realization pair
The detection of gas sensor.
The pH value of acid solution is different, and the doping efficiency of corresponding protonic acid doping to gas sensor is also different,
This results in the efficiency of gas sensor detection gas also different.In a kind of possible embodiment, acid solution
PH value is located in [0.8,1.2] range, to obtain the doping efficiency of preferable Bronsted acid as far as possible.Preferably, the PH of acid solution
When value is 1, doping efficiency is more preferable.
In order to avoid detection of the remaining influence gas sensor to gas of acid solution, the embodiment of the present application is using acid
After solution detects gas sensor, the acid solution for remaining in gas sensor can be removed using alkaline solution.Example
Such as, acid solution is HCL, then alkaline solution can be ammonium hydroxide.
The principle of gas sensor detection gas is described below.
Fig. 8 is referred to, Fig. 8 is the schematic diagram of gas sensor detection gas shown in fig. 6, wherein arrow direction is gas
Body direction.
Gas sensor is placed in gaseous environment, and gas reacts with the gas sensing layer 30 in gas sensor, raw
At proton acid layer 40.The P electron conjugated structure of protonic acid doping in proton acid layer 40 to the polyaniline in gas sensing layer 30
Form p-type and N-type conductive state.The concentration of gas is different, and the amount of Bronsted acid is different, leads to the doping for being doped to styrofoam
Also different, so that two electrodes by gas sensor acquire electric signal, gas is obtained according to electric signal collected
Concentration.
Fig. 9 is referred to, Fig. 9 is the schematic diagram of gas sensor detection gas shown in Fig. 7.Arrow direction is also in Fig. 9
Gas direction, Fig. 9 are only that different with the contact area of gas from the difference of Fig. 8, and testing principle is identical as Fig. 8, here no longer
It repeats.
Based on same invention thought, the embodiment of the present application also provides a kind of gas sensor, which includes
Insulating substrate, gas sensing layer and first electrode and second electrode on insulating substrate；Wherein, gas sensing layer by
Gas sensing material with multiple hole configurationss is formed, and gas sensing material is the polymer of PVDF and PAN；First electrode and
Second electrode is located at the opposite end of the same side of gas sensing layer.Wherein, insulating substrate may include substrate 10, be located at substrate
Grid 101 on 10, and on grid 101 and substrate 10 be arranged 101 side of grid gate insulating layer 20.
Continuing with referring to Fig. 6, in a kind of possible embodiment, first electrode 301 and second electrode 302 are located at gas
Side of the inductive layer 30 far from insulating substrate.
Continuing with referring to Fig. 7, in a kind of possible embodiment, first electrode 301 and second electrode 302 are located at gas
Inductive layer 30 is close to the side of insulating substrate.
In a kind of possible embodiment, insulating substrate is flexible insulating substrate.
Gas sensor in present application example can be obtained by above-mentioned production method, and specific structure can refer to upper
Structure involved in the production method embodiment stated, which is not described herein again.
Obviously, various changes and modifications can be made to the invention without departing from essence of the invention by those skilled in the art
Mind and range.In this way, if these modifications and changes of the present invention belongs to the range of the claims in the present invention and its equivalent technologies
Within, then the present invention is also intended to include these modifications and variations.
Claims (10)
1. a kind of production method of gas sensor characterized by comprising
By Kynoar PVDF and polyaniline PAN, the gas sensing material with multiple hole configurationss is made；
First electrode and second electrode and gas sensing layer are formed on insulating substrate, wherein the first electrode and described
Second electrode is located at the opposite end of the same side of the gas sensing layer, and the gas sensing layer is by the gas sensing material
It is formed.
2. the method as described in claim 1, which is characterized in that by Kynoar PVDF and polyaniline PAN, production has
The gas sensing material of multiple hole configurationss, comprising:
PVDF is dissolved using the first solvent, so that the PVDF has multiple holes；
PAN is adulterated in the PVDF with multiple hole configurationss, forms the gas sensing material.
3. method according to claim 2, which is characterized in that the proportion of first solvent and the PVDF be 50:1~
150:1。
4. method as claimed in claim 2 or claim 3, which is characterized in that first electrode and second electrode are formed on insulating substrate,
And gas sensing layer, comprising:
The gas sensing material is coated on the insulating substrate using spin coating mode, forms the gas sensing layer；
The first electrode and described second are formed far from the opposite end of the insulating substrate side in the gas sensing layer
Electrode.
5. method as claimed in claim 2 or claim 3, which is characterized in that first electrode and second electrode are formed on insulating substrate,
And gas sensing layer, comprising:
Opposite end on the insulating substrate forms the first electrode and the second electrode；
Shape on layer where the gas sensing material is coated in the first electrode and the second electrode using spin coating mode
At the gas sensing layer.
6. the method as described in claim 1, which is characterized in that further include:
The gas sensor is placed in acidic liquid, is detected with the sensitivity to the gas sensor；
Remove the acid solution that the gas sensor carries.
7. method as claimed in claim 6, which is characterized in that the pH value of the acid solution is located in [0.8,1.2] range.
8. a kind of gas sensor characterized by comprising
Insulating substrate；
Gas sensing layer is arranged on the insulating substrate, wherein the gas sensing layer is by the gas with multiple hole configurationss
Body inductive material is formed, and the gas sensing material is the polymer of PVDF and PAN；
First electrode and second electrode, the first electrode and the second electrode are located at the same side of the gas sensing layer
Opposite end.
9. gas sensor as claimed in claim 8, which is characterized in that the first electrode and the second electrode are located at institute
State side of the gas sensing layer far from the insulating substrate；Or,
The first electrode and the second electrode are located at the gas sensing layer close to the side of the insulating substrate.
10. gas sensor as claimed in claim 8 or 9, which is characterized in that the insulating substrate is flexible insulating substrate.
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