CN113804732A - Wearable humidity sensing device for detecting human body sweating rate and manufacturing method thereof - Google Patents
Wearable humidity sensing device for detecting human body sweating rate and manufacturing method thereof Download PDFInfo
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- G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
- G01N27/02—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating impedance
- G01N27/04—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating impedance by investigating resistance
- G01N27/12—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating impedance by investigating resistance of a solid body in dependence upon absorption of a fluid; of a solid body in dependence upon reaction with a fluid, for detecting components in the fluid
- G01N27/125—Composition of the body, e.g. the composition of its sensitive layer
- G01N27/126—Composition of the body, e.g. the composition of its sensitive layer comprising organic polymers
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61B—DIAGNOSIS; SURGERY; IDENTIFICATION
- A61B5/00—Measuring for diagnostic purposes; Identification of persons
- A61B5/42—Detecting, measuring or recording for evaluating the gastrointestinal, the endocrine or the exocrine systems
- A61B5/4261—Evaluating exocrine secretion production
- A61B5/4266—Evaluating exocrine secretion production sweat secretion
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Abstract
The invention discloses a wearable humidity sensing device for detecting the human body sweating rate and a manufacturing method thereof. The humidity sensing device mainly adopts the mechanism that water molecules penetrate into the space between two-dimensional material MXene sheets to cause the tunneling resistance of the water molecules to be increased, and the sensing of humidity response is realized by measuring the resistance. A hydrophilic material, namely sodium poly-styrenate (PAAS), which is extremely sensitive to humidity is doped in the MXene sheet layer, so that the tunneling resistance change between MXene layers is further enhanced. When the mass ratio of the polymer PAAS to the two-dimensional material MXene is 1: when 10, the humidity sensor prepared has the most excellent humidity sensitivity. And the self-assembly fabric hydrophobic layer, the packaging layer, the conductive electrode and the flexible wireless module are combined, so that the service performance and the stability of the humidity sensor can be effectively improved. The humidity sensing device is simple to prepare, low in cost, high in sensitivity, capable of detecting the sweating rate of the human body in different motion states, and capable of being applied to detection of human body breathing parameters, voice recognition and the like.
Description
Technical Field
The invention relates to a wearable humidity sensing device for detecting the human body sweating rate and a manufacturing method thereof.
Background
At present, human attention to body health indexes is getting larger, few wearable devices related to human sweat rate detection are available on the market, and researchers at home and abroad do much work for human sweat detection. Researchers have reported that spraying iodine powder on human skin and contacting with sweat can change the color of the human skin into dark purple, and the iodine powder is used for detecting the existence of the human sweat. However, this method has not been able to assess human sweat levels. In addition, the calculation of the human body's perspiration rate by weighing the patch weight change on the subject is time consuming and does not allow continuous detection of the human body's perspiration rate. Also researchers describe a wearable sweat rate monitoring sensor that is placed at different heights of the skin by two humidity sensors, monitors the humidity at these two heights in real time, and then converts to sweat rate using the first law of fick. However, this device is not flexible and bulky, requiring two different moisture sensors to operate simultaneously, complicating the overall device. And researchers introduce a graphene paper-based pressure sensor with the working range of 0-20kPa, and realize the monitoring of human respiration by depending on the principle that air flow pressurizes the pressure sensor during expiration and reduces pressure during inspiration. Although the work realizes monitoring of respiration, wireless data transmission and remote monitoring cannot be carried out unfortunately, most of wireless modules adopt Bluetooth data transmission at present, and one device can only be connected with one terminal and single-wire data transmission. Besides, the method for monitoring the human breath mainly depends on some heavy and complex instruments such as a pulmonary function instrument, and the high price of the instruments makes the instruments hard to bear by common families. At present, few products related to human body sweating rate monitoring are available on the market, so that the development of a flexible wearable human body sweating rate and respiration monitoring device which is low in price is urgent.
Disclosure of Invention
In order to overcome the technical problems of low sensitivity, small detection range, obvious hysteresis effect, complex device structure and high price of the existing sensor in the monitoring of the human body sweating rate, the invention provides a conductive material, an induction unit, an induction end, a humidity sensor and a manufacturing method thereof in a humidity sensing device, which have the advantages of simple processing and preparation, low production cost and good stability.
In order to achieve the technical purpose, the technical scheme of the invention is that,
a conductive material is prepared by mixing high-molecular polymer sodium poly-styrenate and two-dimensional material MXene.
The mass ratio of the high-molecular polymer sodium polyvinate to the two-dimensional material MXene is 1: 20-1: 5.
The utility model provides a humidity transducer's induction element, adopts conducting material, still include stratum basale and the conducting electrode that insulating material made, conducting material on the at least one side in the two sides of stratum basale of tiling, be equipped with a conducting electrode respectively in the conducting material's of every side tiling both sides.
The utility model provides a humidity transducer's response end adopts the induction element, still include the hydrophobic layer and the encapsulation layer of being made by impervious material, the encapsulation layer including the hydrophobic layer parcel, the hydrophobic layer including the humidity induction element parcel, the hydrophobic layer make by hydrophilic material to the position coating that corresponds humidity induction element has hydrophobic material to form hydrophobic structure, is equipped with the water guide structure that is used for the water guide simultaneously on hydrophobic structure, the encapsulation layer is equipped with the fretwork in the position department that corresponds of water guide structure.
The sensing end of the humidity sensor is characterized in that the water guide structure is a water transportation line structure and comprises at least two water absorption lines which are distributed on a hydrophobic structure at equal intervals and are treated by hydrophilic solution.
A humidity sensor adopts the sensing end of the humidity sensor and further comprises a wireless module, the wireless module is electrically connected with a conductive electrode on the sensing end of the humidity sensor through a wire, the wireless module comprises an Internet of things main control chip, a digital-to-analog conversion chip and a resistance type voltage division circuit, and an electric signal transmitted by the conductive electrode is transmitted to the digital-to-analog conversion chip through the resistance type voltage division circuit and is transmitted to the Internet of things main control chip for uploading after being converted; and one wireless module is at least simultaneously connected with the sensing ends of two humidity sensors.
The utility model provides a humidity sensing device for perspire rate detects, adopts humidity transducer, still include the gauze mask, the gauze mask in correspond the position of mouth nose department and bury the response end that has humidity transducer underground, wireless module has been buried underground to the position that corresponds cheek department in the gauze mask.
A manufacturing method of a conductive material is obtained by mixing high-molecular polymer sodium polyvinate and a two-dimensional material MXene according to a mass ratio of 1: 20-1: 5.
A method for manufacturing a sensing unit of a humidity sensor comprises the following steps:
and 2, coating the conductive material manufactured by the method between the conductive electrodes on the two sides.
A manufacturing method of a sensing end of a humidity sensor comprises the following steps:
step one, based on the area of the sensing unit of the humidity sensor manufactured by the method, a hydrophobic material with the same area is sprayed on a hydrophilic material to form a hydrophobic structure, and a water guide structure is fixed on the hydrophobic structure to obtain a hydrophobic layer;
manufacturing a packaging layer with a two-layer structure through a flexible material, and reserving hollows corresponding to the positions of the water guide structures on the packaging layer;
and step three, clamping the humidity sensing unit of the humidity sensor manufactured by the method between two hydrophobic layers, and then clamping the two hydrophobic layers between two packaging layers to form a sensing end of the humidity sensor.
The manufacturing method of the humidity sensor is based on the sensing end of the humidity sensor manufactured by the method, and further comprises the following steps of:
the method comprises the following steps that a conductive electrode at the sensing end of a humidity sensor and a wireless module are connected with each other through a lead to form a loop, wherein the wireless module comprises an Internet of things main control chip, a digital-to-analog conversion chip and a resistance type voltage division circuit; and the wireless module is at least simultaneously connected with the sensing ends of the two humidity sensors.
The manufacturing method of the humidity sensing device is based on the humidity sensor manufactured by the method, and further comprises the following steps:
a humidity sensor is directly arranged on the surface of a human body and is used as a humidity sensing device for detecting the sweating rate; or
The sensing end of the humidity sensor is embedded in the position, corresponding to the mouth and the nose, of the mask, and the wireless module is embedded in the position, corresponding to the cheek, of the mask, so that the humidity sensing device for sweating rate detection or voice recognition is obtained.
The invention has the technical effects that as MXene has the advantages of high conductivity, good hydrophilicity, rich surface terminals (such as-F and-OH) and the like, the MXene shows hydration in a wider Relative Humidity (RH) range. Water molecules are preferentially adsorbed to the cavities and hydrophilic groups by double or single bonds. After water molecules are inserted into MXene layers, the resistivity is changed, and therefore sensing of humidity is achieved. Based on the purpose of further improving the sensitivity, the hydrophilic and water-swelling material is inserted into the MXene layer, so that the change of the tunneling resistance between the MXene layers can be further increased, and the response sensitivity of the MXene material to humidity is promoted. PAAS (sodium polybenzoate) has good water absorption and expansion properties and is a substance extremely sensitive to humidity. And PAAS is neutral after being dissolved in water, and cannot cause agglomeration or decomposition after being compounded with MXene. Therefore, the compound of MXene and PAAS is very expected to be a humidity-sensitive material with high sensitivity and high response speed. The humidity sensor for detecting the human perspiration rate is manufactured on the basis of the compound, and the principle is that tunneling resistance is increased after water molecules are inserted into MXene layers, so that humidity sensing is realized. When the MXene/PAAS compound humidity sensor used in the invention is exposed in a humidity environment, the interlayer distance of the MXene sheet layer is increased due to water absorption and expansion of PAAS, so that the tunneling resistance of the MXene sheet layer is increased, and the humidity change of the environment is converted into an electric signal visible to people. The humidity sensor is mainly formed by integrating three parts of a high-sensitivity MXene/PAAS humidity sensor, a flexible PDMS membrane and a super-hydrophobic fabric layer. And then the data acquisition in situ and the data transmission in a wireless WiFi mode are realized by connecting the PCB module with the flexible PCB module. The durability of the humidity sensor is effectively improved through the fabric super-hydrophobic layer, the packaging layer, the fabric super-hydrophobic layer, the conductive electrode and the flexible wireless module of the self-assembly structure. Wherein the hydrophobic layer is embedded with a plurality of cotton threads treated with hydrophilic solution in the treated hydrophobic area. The one side that has the cotton thread structure is towards skin, not only can hinder human sweat direct contact humidity transducer through hydrophobic region, also can go out skin accumulation sweat through the cotton thread and transport to hydrophilic region, accomplishes human sweat and detects. On the other hand, the humidity sensor realizes multi-channel wireless data transmission and remote monitoring through a Wifi network established by the flexible wireless module.
Drawings
FIG. 1: schematic structural diagram of device for monitoring sweating rate of MXene/PAAS humidity sensor
FIG. 2: an MXene/PAAS humidity sensor is researched, an experiment chart of the PAAS and the MXene which is a two-dimensional material in the optimal mass ratio is shown, fig. 2(a) shows that the sensitivity of the humidity sensor with different PAAS contents is compared with the sensitivity of the humidity sensor to humidity response, and fig. 2(b) and (c) show that the PAAS response/recovery time is 2mg and 3mg under the 50% RH condition.
FIG. 3: resistance response-time dynamic characteristic curves of the MXene/PAAS humidity sensor under different moderate conditions.
FIG. 4: the MXene/PAAS humidity sensor has dynamic response curves of 19 ℃, 28 ℃, 37 ℃, 40 ℃ and 45 ℃ under the condition of 45% of relative humidity.
FIG. 5: the MXene/PAAS humidity sensor human body perspiration rate monitoring device is attached to the arm in the figure 5 (a); fig. 5(b) forehead; FIG. 5(c) is a graph showing the resistance change versus time characteristic of the back.
FIG. 6: MXene/PAAS humidity sensor, resistance change value and time curve under different hydrophilic/hydrophobic structure fabrics.
FIG. 7: MXene/PAAS humidity sensor, figure 7(a) study the human breath monitoring device when volunteer normally walks, runs, has a rest, lies down the resistance change of deep rest; fig. 7(b) studies the resistance dynamic response curve of MXene/PAAS composite humidity sensor speech recognition.
Wherein, 1 is a basal layer, 2 is a hydrophobic layer provided with a water guide structure, 3 is a packaging layer correspondingly provided with a water guide structure, 4 is a hydrophobic layer without a water guide structure, 5 is a packaging layer correspondingly without a water guide structure, 6 is a lead connecting a wireless module and a conductive electrode, and 7 is a wireless module.
Detailed Description
The foregoing description of the preferred embodiments of the invention will be provided for illustration of the technical solutions adopted to achieve the intended objects and advantages of the invention. It is to be understood that the described embodiments are merely exemplary of the invention, and not restrictive. All other embodiments that can be obtained by a person skilled in the art without making creative efforts based on the embodiments of the present invention belong to the protection scope of the present invention.
First, this embodiment discloses a conductive material, which is formed by mixing high molecular polymer sodium polyvinate and two-dimensional material MXene. Wherein the mass ratio of the high molecular polymer sodium polyvinate to the two-dimensional material MXene is 1: 20-1: 5. The conductive polymer is obtained by doping a two-dimensional conductive material MXene with a high molecular polymer sodium Polybenzoate (PAAS). The sodium poly (styrenate) has good water-swelling property and is a substance extremely sensitive to humidity. And PAAS is neutral after being dissolved in water, and cannot cause agglomeration or decomposition after being compounded with MXene.
Referring to fig. 2, further, the effect on humidity response sensitivity of the humidity sensor by measuring the PAAS content. 0mg, 1mg, 2mg, 3mg and 4mg PAAS are added to obtain MXene/PAAS compound solutions with different PAAS contents, and the relative humidity of 7% is taken as the reference humidity condition of the humidity sensor under the condition of 7% relative humidity. The resistance responses were measured to be 210%, 800%, 1124%, 1080%, 880%, respectively. Therefore, the mass ratio of the polymer PAAS to the two-dimensional material MXene is 1: 10 the sensitivity of the prepared conductive material is highest.
To further derive the effect of PAAS content on humidity response sensitivity of the humidity sensor. Under the condition of 50% relative humidity, the response/recovery time of the resistance of adding 2mg of PAAS is respectively 1.5s and 1.2s, and the response/recovery time of adding 3mg of PAAS is respectively 3.2s and 3.3s, because the added PAAS is excessive, the expansion speed of the film is slowed down due to excessive PAAS content when absorbing water, and the shrinkage recovery capability of the film is weakened due to the confining effect of PAAS on water molecules when dehydrating. Through comparison, the PAAS and MXene mass ratio is 1: and the response speed is quicker when the speed is 10 hours.
Further, the embodiment discloses a sensing unit of a humidity sensor, wherein a conducting material formed by mixing high polymer sodium polyacrylate and a two-dimensional material MXene is coated on a substrate layer made of an insulating material. The substrate layer is sheet-like. And the conductive material may be coated on one or both sides of the base layer. A conductive electrode is provided at each of opposite ends coated with a conductive material so that an independent sensing unit can be formed at each side coated with a conductive material. The substrate layer adopted in the embodiment is a flexible PET substrate, and the thickness is only 0.075mm, so that the substrate has good flexibility and bendability.
Referring to fig. 1, in a further aspect, the present embodiment discloses a sensing end of a humidity sensor, which includes the sensing unit, a hydrophobic layer and an encapsulation layer made of a water-impermeable material, wherein the encapsulation layer encapsulates the hydrophobic layer, the hydrophobic layer encapsulates the humidity sensing unit, the hydrophobic layer is made of a hydrophilic material, the hydrophobic material is coated at a position corresponding to the humidity sensing unit to form a hydrophobic structure, and the hydrophobic structure is provided with a water guide layer for guiding waterThe packaging layer is provided with a hollow part at the corresponding position of the water guide structure. Wherein the hydrophobic layer of this example was made of a fabric and hydrophobic SiO was used at a concentration of 2% wt2The solution is treated to form a hydrophobic structure. The packaging layer is made of Polydimethylsiloxane (PDMS) film. Fig. 1 shows an embodiment in which only one side of the substrate layer is coated with a conductive material and provided with a conductive electrode, so that only one side of the hydrophobic layer is provided with a water guide structure, and when the water guide structure is used, the side provided with the water guide structure faces a position where humidity sensing is required. If both sides have all been coated conducting material, then should all set up the water guide structure on the corresponding hydrophobic layer both sides, humidity sensing can all be carried out to both sides like this.
Further, the water guiding structure of this embodiment is a water transporting line structure, and in this embodiment, 8 water absorbing lines, such as cotton threads or other fabric threads, which are distributed on the hydrophobic structure at equal intervals and treated with a hydrophilic solution are adopted. Hydrophilic SiO for water absorption line2The solution concentration was 3% wt. The gradient equilibrium of wetting can accelerate liquid transport. Cooperate with the hydrophobic layer like this, can effectual protection induction element can not direct contact liquid, can transport the hydrophilic region of hydrophobic layer fabric with the skin sweat of accumulation simultaneously, make humidity transducer can accomplish complete measurement. Therefore, the hydrophobic layer is arranged, so that the device has better air permeability and can well defend against the invasion of dominant sweat from the skin and external liquid, and the sweat accumulated on the skin can be transported to a hydrophilic area through cotton threads. Secondly, the packaging layer is prevented from being directly contacted with the MXene/PAAS compound film to be damaged under the complex human skin bending condition.
Further, this embodiment still discloses a humidity transducer, adopts humidity transducer's response end, still includes wireless module, and wireless module passes through the wire and is connected with the conductive electrode electricity on humidity transducer's the response end, and wireless module includes thing networking main control chip, digital-to-analog conversion chip and hinders formula bleeder circuit, and the signal of telecommunication that conductive electrode transmitted is through hindering formula bleeder circuit and transmitting to digital-to-analog conversion chip to send to thing networking main control chip in order to upload after the conversion. And one wireless module is at least simultaneously connected with the sensing ends of two humidity sensors. The resistance type voltage division circuit is used for converting a resistance signal of the sensor into a voltage signal. The wireless module of the embodiment simplifies circuits on the original Wemos D1mini development version, adds an AD sampling chip, and only uses an ESP8266 chip to communicate with the AD chip through an I2C protocol. The method overcomes the defect that the original ESP chip only has one analog signal channel, and expands into a plurality of channels. And the wireless module directly uses an ESP8266 chip as a main control chip, so that a USB-to-UART circuit, a voltage-stabilized power supply circuit and a switch reset circuit are reduced, and the area of the whole circuit is reduced to 3cm by 2 cm.
Further, this embodiment still discloses a humidity sensing device for perspire rate detects, adopts humidity transducer, still includes the gauze mask, and the position that corresponds mouth nose department in the gauze mask has buried humidity transducer's response end underground, and the position that corresponds cheek department in the gauze mask has buried wireless module underground. The gauze mask that this embodiment adopted is N95 gauze mask, and the humidity sensing device who makes like this can realize the normal position collection and the transmission of wireless wiFi mode of data.
The embodiment also discloses a manufacturing method of the conductive material, which is obtained by directly mixing the high-molecular polymer sodium polyvinlyate and the two-dimensional material MXene according to the mass ratio of 1: 20-1: 5. In this embodiment, the preferable mass ratio of the high molecular polymer sodium polyacrylate to the two-dimensional material MXene is 1: 10.
the embodiment also discloses a manufacturing method of the sensing unit of the humidity sensor, which comprises the following steps:
And 2, coating a conductive material between the conductive electrodes on the two sides. The conductive electrode can be manufactured on one side or two sides of the PET film according to requirements, and the conductive material is correspondingly coated on one side or two sides. In order to make the conductive material better attached to the PET film, the PET film can be subjected to plasma hydrophilic treatment in advance, so that the conductive material can be better combined with the PET film.
The embodiment further discloses a manufacturing method of the sensing end of the humidity sensor, which comprises the following steps:
preparing a hydrophobic layer, respectively weighing 0.789g of hydrophobic silica powder and 1.183g of hydrophilic silica powder, then weighing 50ml of absolute ethyl alcohol, mixing the hydrophobic silica powder and the hydrophilic silica powder, and carrying out ultrasonic treatment for 2h by using an ultrasonic crusher to obtain uniformly dispersed hydrophobic/hydrophilic silica ethanol solution (2 wt% and 3 wt%). The terylene fabric is cut into a rectangle with the size of 24 multiplied by 18mm, a layer of temporary structure cover plate with hollow parts at the positions corresponding to the size and the positions of the induction units is firstly covered on one surface of the cleaned terylene fabric, then the hydrophobic solution containing silicon elements or fluorine elements is sprayed for 20 times in a discontinuous way to ensure that the terylene fabric in the hollow area is super-hydrophobic, and then eight cotton threads which are distributed at intervals and are treated by the hydrophilic solution are embedded in the treated hydrophobic structure area for liquid transportation. If only one side of the PET film is provided with the conductive electrode and the conductive material, the other side of the fabric is only subjected to the same regional super-hydrophobic treatment and is not embedded with cotton threads. The side with the cotton thread structure faces the skin. If both sides of the PET film are provided with the conductive electrodes and the conductive materials, the cotton threads are embedded in both sides of the fabric, namely, both sides can face the skin.
And then manufacturing an encapsulation layer. A two-dimensional plan of the sweat rate monitoring device can be designed by software, and then CO is used according to the designed plan2The marker makes fine engravings on 10X 10cm acrylic plates. CO during engraving2The power of the marking machine is 10W, and the scanning speed is 1200mm s-1And the frequency is set to 8 KHz. The resulting sweat rate test device pattern had a depth of about 500 μm. The acrylic plate with the groove pattern of the sweat rate monitoring device was then washed clean with alcohol and distilled water, respectively, and blown dry with nitrogen.
Mixing a prepolymer of PDMS and a curing agent thereof according to a mass ratio of 10: 1, mixing and stirring uniformly, and then putting the mixture into a vacuum box to remove bubbles in the mixture by using a vacuum pump. The PDMS mixture was then poured into the grooves of an acrylic plate and again bubbled through a vacuum pump and dried at 80 ℃ for 4 h. And then taking down the substrate to obtain an upper cover plate and a lower cover plate which are used as packaging layers, and then ultrasonically cleaning and drying the substrate for later use.
Two electrodes of the MXene/PAAS humidity sensor are respectively welded with a thin copper wire by an electric iron, and then the thin copper wire is clamped between two layers of flexible super-hydrophobic fabrics to form a sandwich structure of the super-hydrophobic fabrics, namely the MXene/PAAS humidity sensor and the super-hydrophobic fabrics. And performing plasma high-grade treatment on the upper cover plate and the lower cover plate of the prepared sweating rate monitoring device for 5min, and packaging the sandwich structure of the super-hydrophobic fabric-MXene/PAAS humidity sensor-super-hydrophobic fabric by using the upper cover plate and the lower cover plate to form a sensing end of the humidity sensor.
The embodiment further discloses a manufacturing method of the humidity sensor, based on the sensing end of the humidity sensor manufactured by the method, the method further comprises the following steps: and connecting a conductive electrode of the humidity sensor with the flexible wireless module through an interface to form a closed loop.
The embodiment further discloses a manufacturing method of a humidity sensing device for detecting sweating rate, which is based on the humidity sensor manufactured by the method, and further comprises the following steps:
the sensing end of the humidity sensor is embedded in the position, corresponding to the mouth and the nose, of the mask, and the wireless module is embedded in the position, corresponding to the cheek, of the mask, so that the humidity sensing device for detecting the sweating rate is obtained.
Referring to fig. 3, the dynamic characteristic of the time-resistance response under different relative humidity conditions. The relative humidity of 7% was used as a reference humidity condition of the humidity sensor, and then the test was performed sequentially from 20% to 80% relative humidity and then from 80% to 20% relative humidity, wherein the relative humidity was maintained for 15 seconds at each relative humidity condition. When the humidity sensor is switched from the relative humidity of 7% to other high humidity conditions, the resistance response quickly reaches a relatively stable value, the quick humidity sensing performance of the humidity sensor is shown, and when the humidity sensor is switched back to the relative humidity of 7% again, the resistance response of the humidity sensor can be quickly restored to the initial state. In addition, the resistance response when the humidity condition is from a low level to a high relative humidity condition is basically symmetrical with the resistance response from the high relative humidity to the low relative humidity, which shows that the resistance response of the MXene/PAAS humidity sensor has good stability under various relative humidity conditions.
Referring to fig. 4, the MXene/PAAS humidity sensor was tested under air humidity conditions (relative humidity of about 45%) with four temperature conditions of 19 ℃, 28 ℃, 37 ℃, 40 ℃ and 45 ℃ respectively set. When the temperature is 19 ℃, the resistance response of the MXene/PAAS humidity sensor is the same as that of the normal condition, the MXene/PAAS humidity sensor has higher response performance, and the resistance response value can reach 152% after three times of continuous tests. The resistance response of the MXene/PAAS humidity sensor decreases with increasing temperature, and when the temperature rises to 45 ℃, the resistance response is only 21%. It is noteworthy that the MXene/PAAS humidity sensor changes responsivity from 46.5% to 36.2% with a response change of only 10% when the temperature is raised from 37 ℃ to 40 ℃. And the temperature change of the human body does not exceed 40 ℃, and the response of the MXene/PAAS humidity sensor is relatively small in the temperature range of 37 ℃ to 40 ℃. Therefore, the MXene/PAAS humidity sensor has great application potential in monitoring the sweating rate of human skin.
Referring to fig. 5, fig. 5a is the sweating rate of the arms of the human body after running and push-up combined exercise for 5 min. Before the volunteer starts to exercise, an MXene/PAAS humidity sensor is directly pasted on the skin to be used as a sweating rate monitoring device for real-time monitoring. After the exercise starts, the phenomenon that the human body does not generate heat when the exercise starts is known in a mode of oral reporting, the human body feels obviously hot after the continuous exercise for 3min, the sweating rate monitoring device starts to have resistance change at the moment, then the human body continues to move for 2min, the resistance change value continues to rise, and the resistance change value starts to fall and returns to the initial state after 7-8k omega. Fig. 5b and 5c monitor the forehead and back sweat rate of a person after exercise, respectively. The volunteers do the same separately as described aboveA combined running and push-up exercise of 5min and it was found that the perspiration rate monitoring device started to increase in resistance value both on the forehead and back of the human body when the volunteer moved to 3 min. After the volunteer completed the 5min exercise, the resistance change value of the sweating rate monitoring device continued to rise, indicating that the volunteer was in a hot state and that the sweating rate was rising. It was then found that the resistance change values of the sweat rate monitoring devices for the forehead and back tested reached 19-20k Ω and 17-18k Ω, respectively, and began to decrease until the initial state was restored. In addition, the experiments show that after the arms, the forehead and the back of the human body are subjected to two times of same exercises, the resistance change values of the sweating rate monitoring device are approximately the same. By simulating the linear relation between the sweating rate and the resistance change value, the resistance change values of the sweating rate monitoring device tested on the arms, the forehead and the back of the human body are converted into the sweating rate information of the human body, and the maximum sweating rate of the arms of the volunteers is found to be 57g/m through analysis2H maximum sweating rate of forehead of 112g/m2H, maximum sweating rate of the back of 104g/m2H. This demonstrates that the sweat rate monitoring device prepared in this example has good monitoring repeatability and reliability.
Referring to fig. 6, fig. 6a shows that when a hydrophilic fabric is used as the lower layer of the humidity sensor under the condition of air humidity of 45%, the tunneling resistance of the humidity sensor increases with the increase of the sweat amount of the volunteer, when the sweat amount increases to be capable of wetting the fabric, the sweat directly contacts the sensor, and the sensor is known to be damaged through the signal of the computer end transmitted by the flexible wireless module. Fig. 6b shows that when the super-hydrophobic fabric is used as the lower layer of the humidity sensor under the same humidity condition, when sweat increases to a certain amount, the super-hydrophobic structure effectively protects the humidity sensor, the tunneling resistance increases first, then becomes flat, and finally decreases along with the sweat evaporation resistance, so that a complete measurement is completed. In consideration of the accumulation of sweat on the super-hydrophobic surface, the embodiment embeds eight hydrophilic cotton threads on the super-hydrophobic structure, so that the accumulated sweat can be transported to a hydrophilic area, and the measurement of the sensor under complex conditions is guaranteed.
Referring to fig. 7, fig. 7a shows that the MXene/PAAS humidity sensor is arranged in the mask as a human bodyThe respiration monitoring device monitors the respiration of the volunteer in different motion states in real time. The resistance of the MXene/PAAS humidity sensor becomes momentarily large when the volunteer exhales through the nose, since the moisture content of the gas exhaled from the human nose is much greater than the moisture content of the environment. When the volunteer inhales, the gas with low external moisture content enters the N95 mask to replace the original gas with high moisture content, and the process is relatively quick, so that the MXene/PAAS humidity sensor resistance is instantly restored to the initial state. When the volunteer breathes normally when walking, the resistance change of 10s is intercepted from the resistance information recorded by the human body respiration monitoring device, wherein three clear resistance peaks with the same contour appear, which indicates that the volunteer breathes 3 times in 10s under normal conditions. The volunteer then started running and the number of resistance peaks increased within 10s, indicating a significant increase in respiratory rate. And after the volunteer sits down and has rested for a few minutes, the frequency of breathing begins to slow down and return to the original normal level. When the volunteer had a deep rest after a trip, the respiratory rate decreased significantly. The volunteer breathes slowly from normal breathing level to breathing quickening to normal breathing finally, and the respiratory information of the human respiration monitoring device recorded in the whole process is very clear, which shows that the device has good stability in the respiration monitoring process. Finally, the duration of exhalation was summarized as 2.3s, 1s, 2.2s and 3.7s and the duration of inhalation was summarized as 1.2s, 0.7s, 1.1s and 2.5s for the volunteers in normal state, running state, rest and lying down deep rest. According to the formula Rres＝60/(Tex+Tin) Wherein R isresRepresenting the breathing rate, TexRepresenting the expiratory interval, TinRepresenting the inspiration interval time. Thereby obtaining the breathing rate of 16min when the volunteer is in a normal state, a running state, a rest state and a lying-down deep rest state-1、38min-1、17min-1And 10min-1. These results indicate that the MXene/PAAS humidity sensor has great potential for monitoring human respiration in real time.
FIG. 7b shows that the volunteer speaks "Humidity" and "Sensor" twice in succession towards the MXene/PAAS moisture Sensor, resulting in the MXene/PAAS moisture Sensor clearly and completely recording the voice information of the volunteer speaking. The three resistance peaks recorded by the MXene/PAAS Humidity Sensor exhibited a gradual decline trend when the volunteer said "Humidity" twice, while the three resistance peaks recorded by the MXene/PAAS Humidity Sensor were at substantially the same resistance level when the "Sensor" was said twice. The MXene/PAAS humidity sensor disclosed by the embodiment can be used for voice recognition of people due to different characteristic peaks of the resistance.
This example discloses the preparation of a MXene/PAAS wearable humidity sensor on a flexible two-electrode PET substrate using drop coating with response/recovery times of 1.5s and 1.2s, respectively, and a maximum resistance response of 1124%. The humidity sensor disclosed by the embodiment can be used for detecting the sweating rate of a human body in different motion states, and can also be applied to detection of respiratory parameters, voice recognition and the like of the human body. Meanwhile, the method has the characteristics of simple processing and preparation, low production cost, good stability and the like.
Claims (12)
1. The conductive material is characterized by being formed by mixing high-molecular polymer sodium polyvinate and a two-dimensional material MXene.
2. The conductive material of claim 1, wherein the mass ratio of the high molecular polymer sodium polyacrylate to the two-dimensional material MXene is 1:20 to 1: 5.
3. A sensing element of a humidity sensor, comprising the conductive material of claim 1 or 2, a substrate layer made of an insulating material, and a conductive electrode, wherein the conductive material is laid on at least one of two sides of the substrate layer, and one conductive electrode is provided on each side of the laid conductive material.
4. The sensing end of the humidity sensor is characterized in that the sensing unit according to claim 3 is adopted, the sensing unit further comprises a hydrophobic layer and an encapsulation layer made of a water-impermeable material, the encapsulation layer wraps the hydrophobic layer, the hydrophobic layer wraps the humidity sensing unit, the hydrophobic layer is made of a hydrophilic material, the position corresponding to the humidity sensing unit is coated with a hydrophobic material to form a hydrophobic structure, meanwhile, a water guide structure used for guiding water is arranged on the hydrophobic structure, and the encapsulation layer is provided with a hollow part at the position corresponding to the water guide structure.
5. The sensing end of claim 4, wherein the water guiding structure is a water carrying line structure, and comprises at least two water absorbing lines disposed on the hydrophobic structure at equal intervals and treated with a hydrophilic solution.
6. A humidity sensor is characterized in that the sensing end of the humidity sensor according to any one of claims 4 to 5 is adopted, and the humidity sensor further comprises a wireless module, the wireless module is electrically connected with a conductive electrode on the sensing end of the humidity sensor through a lead, the wireless module comprises an Internet of things main control chip, a digital-to-analog conversion chip and a resistance type voltage division circuit, and an electric signal transmitted by the conductive electrode is transmitted to the digital-to-analog conversion chip through the resistance type voltage division circuit and is transmitted to the Internet of things main control chip for uploading after being converted; and one wireless module is at least simultaneously connected with the sensing ends of two humidity sensors.
7. A humidity sensing device for detecting the sweating rate is characterized in that the humidity sensor according to claim 6 is adopted, the humidity sensing device further comprises a mask, a sensing end of the humidity sensor is embedded in a position, corresponding to the mouth and nose, in the mask, and a wireless module is embedded in a position, corresponding to the cheek, in the mask.
8. The manufacturing method of the conductive material is characterized by mixing high-molecular polymer sodium polyvinate and a two-dimensional material MXene according to the mass ratio of 1: 20-1: 5.
9. A method for manufacturing a sensing unit of a humidity sensor is characterized by comprising the following steps:
step 1, coating conductive substances on two opposite sides of at least one surface of an insulating material serving as a substrate layer respectively, and fixing a conductor on the conductive substances to obtain a conductive electrode;
step 2, coating the conductive material prepared by the method of claim 8 between the conductive electrodes on both sides.
10. A manufacturing method of a sensing end of a humidity sensor is characterized by comprising the following steps:
firstly, based on the area of the sensing unit of the humidity sensor manufactured by the method of claim 9, spraying hydrophobic materials with the same area on a hydrophilic material to form a hydrophobic structure, and fixing a water guide structure on the hydrophobic structure to obtain a hydrophobic layer;
manufacturing a packaging layer with a two-layer structure through a flexible material, and reserving hollows corresponding to the positions of the water guide structures on the packaging layer;
step three, sandwiching the humidity sensing unit of the humidity sensor manufactured by the method according to claim 9 between two hydrophobic layers, and then sandwiching the two hydrophobic layers between two encapsulation layers to form a sensing end of the humidity sensor.
11. A method for manufacturing a humidity sensor, wherein the sensing terminal of the humidity sensor manufactured by the method according to claim 10 further comprises the following steps:
the method comprises the following steps that a conductive electrode at the sensing end of a humidity sensor and a wireless module are connected with each other through a lead to form a loop, wherein the wireless module comprises an Internet of things main control chip, a digital-to-analog conversion chip and a resistance type voltage division circuit; and the wireless module is at least simultaneously connected with the sensing ends of the two humidity sensors.
12. A method of manufacturing a humidity sensor device, based on the humidity sensor manufactured by the method of claim 11, further comprising the steps of:
a humidity sensor is directly arranged on the surface of a human body and is used as a humidity sensing device for detecting the sweating rate; or
The sensing end of the humidity sensor is embedded in the position, corresponding to the mouth and the nose, of the mask, and the wireless module is embedded in the position, corresponding to the cheek, of the mask, so that the humidity sensing device for sweat rate detection or voice recognition is obtained.
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