CN111879838A - Flexible paper-based voltage type humidity sensor and preparation method thereof - Google Patents
Flexible paper-based voltage type humidity sensor and preparation method thereof Download PDFInfo
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Images
Classifications
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
- G01N27/26—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating electrochemical variables; by using electrolysis or electrophoresis
- G01N27/416—Systems
Abstract
The invention discloses a flexible paper-based voltage type humidity sensor and a preparation method thereof, belongs to the technical field of humidity sensitive elements, and aims to overcome the defect that the traditional resistance and capacitance type humidity sensor needs to supply power for working, and the method comprises the following steps: soaking paper in an electrolyte solution, fully wetting and drying to obtain a paper humidity sensitive layer containing electrolyte; and combining the positive electrode and the negative electrode on the surface of the paper humidity sensitive layer, and connecting a test lead to obtain the flexible paper-based voltage type humidity sensor. The flexible paper-based voltage type humidity sensor has the advantages of extremely simple preparation process, low cost and easy batch production; the power supply has the advantages of spontaneously generated voltage and zero power consumption; the detection of different humidity is realized by testing the voltage signals at two ends of the sensor electrode along with the change of humidity, and the flexible paper-based voltage type humidity sensor has wide application prospect in the aspect of environment humidity detection.
Description
Technical Field
The invention discloses a flexible paper-based voltage type humidity sensor and a preparation method thereof, belongs to the technical field of humidity sensitive elements, and particularly relates to the technical field of humidity sensors.
Background
Humidity sensors have important applications in industrial, agricultural, household, and medical settings. Currently, commercial humidity sensors are mainly of a resistance type and a capacitance type, and can work only by an external power supply. With the development of wireless sensor networks, internet of things and wearable electronics, higher requirements are put forward on the energy consumption of the humidity sensor, and the humidity sensor with low power consumption or even no power consumption is urgently needed.
Patent No. CN201611075380.0 discloses a voltage type humidity sensor, which comprises a sensing unit containing a humidity sensitive element and a detection circuit, an energy storage unit containing a rectification circuit and an energy storage element, and a friction power generation device consisting of a first friction part and a second friction part, wherein the friction power generation device is used as a passive power supply unit; the self-powered sensor has reasonable structural design, and can integrate the energy collection and conversion function and the humidity detection function into a whole; the design of the elastic supporting structure not only enables the output voltage of the power supply unit to be adjustable, but also is convenient to maintain and saves cost through detachable connection; in addition, the sensor of the invention has simple manufacturing method and low cost, and can realize industrial production and large-scale application. However, the device is based on the principle of triboelectrification, external continuous mechanical vibration is needed to drive the humidity sensor to generate electricity, and the device cannot work when no mechanical vibration exists.
Patent No. CN201910051173.9 discloses a wet gas power generation method and apparatus, the method includes the following steps: pouring the polymer solution into a culture dish, and then placing the culture dish into an oven to prepare a polymer power generation membrane; arranging a polymer power generation film on a moisture-insulated metal electrode, and arranging a porous top electrode above the polymer power generation film to protect the film form of the polymer power generation film and transmit moisture; the separation of positive and negative ion pairs in the polymer power generation membrane is induced by applying moisture stimulation to the exterior of the metal electrode in a single direction, and freely moving carriers are released; electric potential difference and electric current are generated by diffusion of carriers from a high concentration to a low concentration region, thereby outputting electric energy to the outside. The method adopts a high polymer material which is simple and easy to obtain, can be bent, stretched and even self-repaired, simultaneously adopts directional moisture stimulation to realize moisture control, does not need to use expensive laser, has simple testing means, does not need to use other expensive external equipment in the testing process, and has the advantage of large-scale integration. The device is based on the principle of ion generation and diffusion, and relies on humidity to induce the separation of positive and negative ion pairs inside the polymer power generation membrane to generate voltage, however, the raw materials involved in the technology are expensive and need a complex pretreatment process, and the device preparation cost is high, so that the device is not beneficial to practical application.
Disclosure of Invention
The invention aims to: the flexible paper-based voltage type humidity sensor and the preparation method thereof are provided to solve the defect that the traditional resistance and capacitance type humidity sensor needs power supply work.
A preparation method of a flexible paper-based voltage type humidity sensor comprises the following steps:
(1) soaking paper in an electrolyte solution, fully wetting, and drying at 20-60 ℃ for 1-10 hours to obtain a paper moisture sensitive layer containing electrolyte;
(2) and combining the positive electrode and the negative electrode on the surface of the paper humidity sensitive layer, and connecting a test lead to obtain the flexible paper-based voltage type humidity sensor.
The working principle is as follows: the flexible paper-based voltage type humidity sensor is based on the power generation principle of a primary battery and the moisture absorption characteristic of paper, and the two ends of a positive electrode and a negative electrode of the humidity sensor can spontaneously generate oxidation-reduction reaction, wherein the positive electrode generates reduction reaction and the negative electrode generates oxidation reaction. After the paper with hygroscopicity adsorbs water molecules, the redox reaction rates of the positive electrode and the negative electrode can be enhanced, and the adsorbed water molecules play a role of an ion transmission channel, so that the ion transmission rate between the positive electrode and the negative electrode can be improved, the voltage at the two ends of the positive electrode and the negative electrode is increased, and different humidities can be known by testing the voltage between the two ends of the positive electrode and the negative electrode of the humidity sensor.
Specifically, taking an aluminum-copper electrode-sodium chloride electrolyte paper-based humidity sensor as an example, aluminum is taken as a negative electrode, electron loss is oxidized, 4Al-12e-═4Al3+(ii) a Copper as positive electrode, oxygen in environment is reduced to 6H2O+12e-+3O2═12OH-(ii) a Total reaction formula of 4Al +6H2O+3O2＝4Al(OH)3。
Concretely, taking a zinc-copper electrode-dilute hydrochloric acid electrolyte paper-based humidity sensor as an example, zinc is taken as a negative electrode, electron loss is oxidized, and Zn-2e-═Zn2+(ii) a Copper as positive electrode, reducing the hydrogen ions in diluted hydrochloric acid to obtain electrons 2H++2e-═H2(ii) a General reaction formula Zn +2H+═Zn2++H2。
Specifically, taking an aluminum-magnesium electrode-sodium hydroxide electrolyte paper-based humidity sensor as an example, aluminum is taken as a negative electrode, electron loss is oxidized, 2Al-6e-+8OH-═2(AlO2)-+4H2O; magnesium as positive electrode, reduction of generated water 6H2O+6e-═6OH-+3H2(ii) a The total reaction formula is 2Al +2OH-+2H2O═2(AlO2)-+3H2。
In the present application: the flexible paper-based voltage type humidity sensor has the advantages of extremely simple preparation process, low cost and easy batch production; the humidity monitoring system has the advantages of spontaneously generating voltage and zero power consumption, and is expected to realize a large-scale wireless humidity monitoring sensing network; the detection of different humidity is realized by testing the voltage signals at the two ends of the sensor electrode along with the change of the humidity, and the method has wide application prospect in the aspects of humidity detection of environments such as weather, industry, agriculture, home furnishing and the like; in addition, the flexible paper-based voltage type humidity sensor has the flexible characteristic, and can be used in the flexible wearable fields of respiratory frequency monitoring, non-contact switching, skin humidity monitoring, baby diaper monitoring and the like.
Preferably, the electrolyte in step (1) comprises any one of hydrochloric acid, sulfuric acid, carbonic acid, nitric acid, sodium hydroxide, calcium hydroxide, ammonia water, sodium chloride, lithium chloride, potassium chloride or barium sulfate.
Preferably, the solvent of the electrolyte is water.
Preferably, the concentration of the electrolyte is 0 to 5 mol/L.
Preferably, the positive electrode material is any one of graphite, magnesium, manganese, iron, nickel, lead, copper, silver, platinum, or gold.
Preferably, the negative electrode material is any one of lithium, aluminum, manganese, zinc, cadmium, or iron.
Preferably, copper is the positive electrode and zinc is the negative electrode.
Preferably, copper is the positive electrode and aluminum is the negative electrode.
Preferably, graphite is the positive electrode and zinc is the negative electrode.
Preferably, graphite is the positive electrode and aluminum is the negative electrode.
Preferably, magnesium is the positive electrode and aluminum is the negative electrode.
Preferably, the paper includes any one of filter paper, printing paper, writing paper, wrapping paper, cardboard, or toilet paper.
Preferably, in the step (2), the method for bonding the electrode to the paper is any one of pasting, evaporation, printing, sputtering and coating.
Preferably, the positive electrode and the negative electrode are on the same side of the paper moisture sensitive layer, and the distance between the positive electrode and the negative electrode is 1-20 mm.
Preferably, the positive and negative electrodes are on either side of the paper moisture sensitive layer.
Preferably, the paper is filter paper, the electrolyte solution is 1 mo/L sodium chloride solution, and the wetted electrolyte paper is dried at 50 ℃ for 1 hour.
Preferably, the positive electrode material is copper foil, the negative electrode material is aluminum foil, and the copper foil and the aluminum foil are adhered to the surface of the filter paper, wherein the electrode distance is 5 mm.
The flexible paper-based voltage type humidity sensor obtained by the preparation method of the flexible paper-based voltage type humidity sensor comprises a paper humidity sensitive layer, wherein a positive electrode and a negative electrode are arranged on the surface of the paper humidity sensitive layer, and test leads are respectively arranged on the positive electrode and the negative electrode.
In summary, due to the adoption of the technical scheme, the invention has the beneficial effects that:
1. in the invention, the flexible paper-based voltage type humidity sensor has the advantages of extremely simple preparation process, low cost and easy batch production;
2. the power supply has the advantages of spontaneously generated voltage and zero power consumption;
3. the detection of different humidity is realized by testing the voltage signals at the two ends of the sensor electrode along with the change of the humidity, and the method has wide application prospect in the aspect of environment humidity detection;
4. the flexible paper-based voltage type humidity sensor has the flexible characteristic and can be used in the field of flexible wearability.
Drawings
FIG. 1 is a schematic diagram of the structure of a flexible paper-based voltage type humidity sensor with electrodes on the same side;
FIG. 2 is a schematic diagram of the structure of the flexible paper based voltage type humidity sensor electrode of the present invention on both sides;
FIG. 3 is a graph of the voltage response of a humidity sensor at different humidities according to one embodiment of the present invention;
FIG. 4 is a graph of 4 cycle responses of a humidity sensor with 0% and 91.5% relative humidity switching with electrodes connected in the forward direction according to one embodiment of the present invention;
FIG. 5 is a graph of 4 cycle responses of a humidity sensor with 0% and 91.5% relative humidity switching with electrode reverse connections according to one embodiment of the present invention;
FIG. 6 is a graph of humidity sensor response to different breathing frequencies according to one embodiment of the present invention.
The labels in the figure are: 1-paper moisture sensitive layer, 2-positive electrode, 3-negative electrode, 4-wire.
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 specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
Example 1
Referring to fig. 1, a flexible paper-based voltage type humidity sensor comprises a paper humidity sensitive layer 1, wherein a positive electrode 2 and a negative electrode 3 are arranged on the surface of the paper humidity sensitive layer 1, a test lead 4 is respectively arranged on the positive electrode 2 and the negative electrode 3, and the paper humidity sensitive layer 1 contains electrolyte; the paper is filter paper; the anode material is copper, and the cathode material is aluminum; the electrolyte solution is 0 mol/L sodium chloride solution, and the positive electrode 2 and the negative electrode 3 are combined with the paper humidity sensitive layer 1 through a pasting process; the positive electrode 2 and the negative electrode 3 are arranged on the same side of the paper moisture sensitive layer 1, and the distance between the positive electrode 2 and the negative electrode 3 is 1 mm.
Example 2
On the basis of example 1, the electrolyte solution was 0.5 mo/L sodium chloride solution; the positive electrode 2 and the negative electrode 3 were spaced apart by 5mm, and the rest was the same as in example 1.
Example 3
On the basis of example 1, the electrolyte solution was 0.5 mo/L sodium chloride solution; the positive electrode 2 and the negative electrode 3 were spaced apart by 10mm, and the rest was the same as in example 1.
Example 4
On the basis of example 1, the electrolyte solution is a 5 mo/L sodium chloride solution; the positive electrode 2 and the negative electrode 3 were spaced apart by 20mm, and the rest was the same as in example 1.
In examples 1 to 4, the paper may be any of printing paper, writing paper, wrapping paper, cardboard, or toilet paper.
Examples 1-4, copper-zinc primary cells were used: copper is used as the anode, and zinc is used as the cathode; graphite-zinc galvanic cell: graphite is used as a positive electrode, and zinc is used as a negative electrode; graphite-aluminum galvanic cell: graphite is used as a positive electrode, and aluminum is used as a negative electrode; magnesium-aluminum primary cell: magnesium is used as the positive electrode, and aluminum is used as the negative electrode.
As shown in FIG. 2, in examples 1 to 4, the positive electrode 2 and the negative electrode 3 are on both sides of the paper moisture sensitive layer 1.
In examples 1 to 4, the electrolyte is any of hydrochloric acid, sulfuric acid, carbonic acid, nitric acid, sodium hydroxide, calcium hydroxide, ammonia water, lithium chloride, potassium chloride, or barium sulfate.
In examples 1 to 4, the method of bonding the positive electrode 2 or the negative electrode 3 to the paper is any one of evaporation, printing, sputtering, or coating.
Example 5
A preparation method of a flexible paper-based voltage type humidity sensor comprises the following steps:
(1) soaking filter paper in 1mol/L sodium chloride electrolyte solution, fully wetting, and drying at 50 ℃ for 1 hour to obtain a paper humidity-sensitive layer 1 containing sodium chloride electrolyte;
(2) and (3) adhering a copper foil made of the material of the positive electrode 2 and an aluminum foil made of the material of the negative electrode 3 on the surface of the same side of the filter paper humidity-sensitive layer, wherein the electrode distance is 5mm, and connecting a test lead 4 to obtain the flexible paper-based voltage type humidity sensor.
Example 6
In the step (1), the paper was immersed in 2mol/L sodium chloride electrolyte solution, and the rest was the same as in example 5.
Example 7
In the step (2), a copper electrode and an aluminum electrode are prepared on the surface of the filter paper by adopting an evaporation process, and the rest is the same as that of the embodiment 5.
Examples of the experiments
According to the flexible paper-based voltage type humidity sensor prepared in the examples 1 and 5, performance test is carried out according to the method disclosed in the field, and the specific method is as follows: (a) the voltage signals of the humidity sensors prepared above were tested with a gishley KEI THLEY 6514 electrometer, and different relative humidity environments were obtained by the bubbling method and calibrated with high precision humidity sensors, and the Relative Humidity (RH) included 0%, 18.7%, 41.1%, 60.8%, 79.3% and 91.5%; (b) in order to prove the application of the humidity sensor, the humidity sensor is attached to the mouth and the nose, different breathing frequencies are simulated, the output voltage of the humidity sensor is collected, and a human body breathing frequency voltage curve can be obtained.
As shown in FIG. 3, the voltage response of the humidity sensor at different humidities shows that the humidity sensor has different response voltages at different humidities.
From the 4-cycle response diagram of the humidity sensor of fig. 4 under the switching of 0% and 91.5% RH with the positive electrode connection, the output voltage of the humidity sensor is a positive voltage, the voltage increases positively with the increase of humidity, the good response recovery characteristic is shown, and the principle of the voltage generation of the primary battery is conformed.
From the 4 cycle response graphs of the humidity sensor in fig. 5 under the condition that the electrodes are positively connected and the 0% and 91.5% RH are switched, the output voltage of the humidity sensor is negative, the voltage is increased in the negative direction along with the increase of the humidity, the good response recovery characteristic is shown, and the principle of the voltage generated by the primary battery is met.
As shown in FIG. 6, the response curve of the humidity sensor to different respiratory frequencies shows that the humidity sensor can be used in the fields of respiratory frequency monitoring, medical health and the like.
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 (10)
1. A preparation method of a flexible paper-based voltage type humidity sensor is characterized by comprising the following steps:
(1) soaking paper in an electrolyte solution, fully wetting, and drying at 20-60 ℃ for 1-10 hours to obtain a paper moisture sensitive layer containing electrolyte;
(2) and combining the positive electrode and the negative electrode on the surface of the paper humidity sensitive layer, and connecting a test lead to obtain the flexible paper-based voltage type humidity sensor.
2. The method for preparing a flexible paper-based voltage type humidity sensor according to claim 1, wherein the electrolyte in the step (1) comprises any one of hydrochloric acid, sulfuric acid, carbonic acid, nitric acid, sodium hydroxide, calcium hydroxide, ammonia water, sodium chloride, lithium chloride, potassium chloride or barium sulfate.
3. The method for preparing a flexible paper-based voltage type humidity sensor according to claim 2, wherein the solvent of the electrolyte is water.
4. The method for preparing a flexible paper-based voltage type humidity sensor according to claim 1 or 3, wherein the concentration of the electrolyte is 0-5 mol/L.
5. The method for preparing the flexible paper-based voltage type humidity sensor according to claim 1, wherein the positive electrode material is any one of graphite, magnesium, manganese, iron, nickel, lead, copper, silver, platinum or gold.
6. The method for preparing the flexible paper-based voltage type humidity sensor according to claim 1, wherein the negative electrode material is any one of lithium, aluminum, manganese, zinc, cadmium or iron.
7. The method for preparing a flexible paper-based voltage type humidity sensor according to claim 1, wherein the paper comprises any one of filter paper, printing paper, writing paper, wrapping paper, paperboard or toilet paper.
8. The method for preparing a flexible paper-based voltage type humidity sensor according to claim 1, wherein the positive electrode and the negative electrode are on the same side of the paper humidity sensitive layer, and the distance between the positive electrode and the negative electrode is 1-20 mm.
9. The method for preparing a flexible paper-based voltage type humidity sensor according to claim 1, wherein the positive electrode and the negative electrode are on both sides of the paper humidity sensitive layer.
10. A flexible paper-based voltage type humidity sensor obtained by the preparation method of the flexible paper-based voltage type humidity sensor according to any one of claims 1 to 9, which is characterized by comprising a paper humidity sensitive layer, wherein the surface of the paper humidity sensitive layer is provided with a positive electrode and a negative electrode, and the positive electrode and the negative electrode are respectively provided with a test lead.
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