CN111442861A - Wearable bionic piezoresistive sensor and preparation method and application thereof - Google Patents
Wearable bionic piezoresistive sensor and preparation method and application thereof Download PDFInfo
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- CN111442861A CN111442861A CN202010289096.3A CN202010289096A CN111442861A CN 111442861 A CN111442861 A CN 111442861A CN 202010289096 A CN202010289096 A CN 202010289096A CN 111442861 A CN111442861 A CN 111442861A
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01L—MEASURING FORCE, STRESS, TORQUE, WORK, MECHANICAL POWER, MECHANICAL EFFICIENCY, OR FLUID PRESSURE
- G01L1/00—Measuring force or stress, in general
- G01L1/18—Measuring force or stress, in general using properties of piezo-resistive materials, i.e. materials of which the ohmic resistance varies according to changes in magnitude or direction of force applied to the material
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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
- A61B5/103—Detecting, measuring or recording devices for testing the shape, pattern, colour, size or movement of the body or parts thereof, for diagnostic purposes
- A61B5/11—Measuring movement of the entire body or parts thereof, e.g. head or hand tremor, mobility of a limb
- A61B5/1126—Measuring movement of the entire body or parts thereof, e.g. head or hand tremor, mobility of a limb using a particular sensing technique
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61B—DIAGNOSIS; SURGERY; IDENTIFICATION
- A61B5/00—Measuring for diagnostic purposes; Identification of persons
- A61B5/68—Arrangements of detecting, measuring or recording means, e.g. sensors, in relation to patient
- A61B5/6801—Arrangements of detecting, measuring or recording means, e.g. sensors, in relation to patient specially adapted to be attached to or worn on the body surface
- A61B5/6802—Sensor mounted on worn items
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01L—MEASURING FORCE, STRESS, TORQUE, WORK, MECHANICAL POWER, MECHANICAL EFFICIENCY, OR FLUID PRESSURE
- G01L9/00—Measuring steady of quasi-steady pressure of fluid or fluent solid material by electric or magnetic pressure-sensitive elements; Transmitting or indicating the displacement of mechanical pressure-sensitive elements, used to measure the steady or quasi-steady pressure of a fluid or fluent solid material, by electric or magnetic means
- G01L9/02—Measuring steady of quasi-steady pressure of fluid or fluent solid material by electric or magnetic pressure-sensitive elements; Transmitting or indicating the displacement of mechanical pressure-sensitive elements, used to measure the steady or quasi-steady pressure of a fluid or fluent solid material, by electric or magnetic means by making use of variations in ohmic resistance, e.g. of potentiometers, electric circuits therefor, e.g. bridges, amplifiers or signal conditioning
- G01L9/06—Measuring steady of quasi-steady pressure of fluid or fluent solid material by electric or magnetic pressure-sensitive elements; Transmitting or indicating the displacement of mechanical pressure-sensitive elements, used to measure the steady or quasi-steady pressure of a fluid or fluent solid material, by electric or magnetic means by making use of variations in ohmic resistance, e.g. of potentiometers, electric circuits therefor, e.g. bridges, amplifiers or signal conditioning of piezo-resistive devices
Abstract
The invention discloses a wearable bionic piezoresistive sensor and a preparation method and application thereof. The sensor comprises a three-dimensional sponge composite framework, an electrode and a detection instrument; the electrodes are arranged on two sides of the three-dimensional sponge composite framework; the detection instrument is connected with the electrode through a lead; MXene is filled in the three-dimensional sponge composite framework. MXene is dispersed in water, then three-dimensional sponge is soaked in dispersion liquid for multiple times and dried to prepare three-dimensional conductive sponge, and finally, two ends of the three-dimensional conductive sponge are wrapped by electrodes, and the electrodes are connected with a measuring instrument through leads. According to the invention, the sensor with high sensitivity is prepared by constructing the micro-crack structure on the surface of the three-dimensional sponge. The sensor can be used for rapidly detecting the motion process of a human body, has the advantages of simple preparation process, low cost, high sensitivity, short response time and better repeatability in more than 500 cycles, and opens up a new opportunity for the application of the sensor.
Description
Technical Field
The invention belongs to the field of sensors, and particularly relates to a wearable bionic piezoresistive sensor and a preparation method and application thereof.
Background
Flexible and high-sensitivity pressure sensors are of great interest due to their wide range of applications, such as potential applications in motion detection, electronic skin, biosensors, etc. In recent years, various pressure sensing mechanisms including transistor sensing, capacitive sensing, piezoelectric sensing, triboelectric sensing, and particularly resistive sensing, have been developed to construct sensitive pressure sensors. On the other hand, a reasonable micro-or nano-structured design also plays an important role in the manufacture of innovative pressure sensors.
Spiders are the species of the animal community most sensitive to ambient vibrations. Their most important vibration detectors are based on a crack-like slit system near the leg joint between the metatarsal and tarsal bones. Inspired by sensor systems, various crack-based sensors have been developed in recent years, including gas sensors, torsion sensors, and particularly strain sensors. Conventional piezoresistive pressure sensors are based on component metals and semiconductor materials and have high sensitivity, but can only detect a narrow strain range due to their inherent rigidity and high conductivity. At present, the bionic sensor, especially the flexible wearable sensor, is researched less domestically. With the rapid development of artificial intelligence technology, the demand for sensor materials is also increasing. Therefore, it remains a great challenge to manufacture wearable piezoresistive sensing materials that meet a wide range of standards and are cost-effective.
Disclosure of Invention
The invention aims to provide a wearable bionic piezoresistive sensor and a preparation method and application thereof, aiming at the defects of the prior art. The preparation process is simple, energy-saving and environment-friendly, and has good application prospect. The sensitivity of the sensor is improved by applying the bionics principle, and the piezoresistive sensor with high sensitivity is prepared.
The purpose of the invention is realized by the following technical scheme.
A wearable bionic piezoresistive sensor comprises a three-dimensional sponge composite framework, electrodes and a detection instrument; the electrodes are arranged on two sides of the three-dimensional sponge composite framework; the detection instrument is connected with the electrode through a lead; transition metal carbide MXene is filled in the three-dimensional sponge composite framework.
The working range of the wearable bionic piezoresistive sensor is 0-30KPa, the response time is 30-60ms, the relaxation time is 150-200ms, and the wearable bionic piezoresistive sensor still has good detectability after 500 times of cyclic compression.
Preferably, the transition metal carbide MXene is Ti3C2，Ti2C，Ti4C3，V3C2And V2One or more of C, more preferably Ti3C2。
Preferably, the three-dimensional sponge in the three-dimensional sponge composite framework is made of polyurethane.
Preferably, the electrode is made of copper foil or conductive silver paste; the lead is an iron wire, a copper wire or a silver wire.
The preparation method of the wearable bionic piezoresistive sensor comprises the following steps:
(1) weighing transition metal carbide MXenes, dispersing in water, and performing ultrasonic homogenization to obtain transition metal carbide MXenes dispersion liquid; soaking the three-dimensional sponge in MXene dispersion liquid of transition metal carbide, and vacuumizing and filling to enable the three-dimensional sponge to be filled with MXene;
(2) drying the three-dimensional sponge prepared in the step (1) to obtain a three-dimensional conductive sponge, and marking the three-dimensional conductive sponge as MXene @ PU;
(3) and packaging the two ends of MXene @ PU by using electrode materials, and connecting the electrode materials with a detection instrument through a wire to obtain the wearable bionic piezoresistive sensor.
Preferably, the ultrasonic treatment in the step (1) is carried out by using a cell crushing ultrasonic machine, the power of the ultrasonic treatment is 60W-80W, more preferably 70W, and the time is 1-3 h; the number of times of vacuum pumping is 3-5.
Preferably, the mass ratio of the transition metal carbide MXene to the water in the step (1) is (1-3): 70-90, and more preferably (1-2): 80.
Preferably, the three-dimensional sponge is made of polyurethane PU, and is 12cm long, 2cm wide and 1cm thick.
Preferably, the drying temperature in the step (2) is 60-100 ℃, more preferably 80 ℃, and the drying time is 3-5 h.
Preferably, in the step (2), the soaking and drying process is repeated after the three-dimensional sponge is dried, and the soaking and drying times are 1 to 5 times, and more preferably 3 times.
The wearable bionic piezoresistive sensor is applied to the preparation of a human motion detection device.
Preferably, the human body movement includes a fist, a wrist bend, a finger movement and an exhalation.
The invention applies the transition metal carbide to the field of sensors, and has the advantages of improving the combination of a substrate and an interface, improving the sensitivity and stability of the sensor to a great extent, and the like. And the preparation process is environment-friendly, efficient and energy-saving, can be suitable for lower working voltage, and opens up a new opportunity for the wide application of the sensor.
Compared with the prior art, the invention has the following advantages:
1. bionic: the sensor prepared by the invention imitates slit-shaped organs on spider legs, and the sensitivity and the working range of the sensor are greatly improved by constructing a micro-crack structure on the surface of the sponge.
2. Simple and environment-friendly: the piezoresistive sensor is prepared by selecting the transition metal carbide MXene material, and the piezoresistive sensor has multiple effects of simple preparation process operation, no environmental pollution, low cost and the like.
3. And (4) multiple functions: the piezoresistive sensor prepared by the invention can be used for monitoring various movements of a human body in real time, such as wrist bending finger movement, expiration and the like.
4. The raw materials are saved: the invention has the advantages of lower reaction temperature, short reaction time, energy saving, less raw materials and high efficiency.
Drawings
FIG. 1a is a schematic diagram of the preparation of MXene @ PU sponge in example 1 of the present invention.
FIG. 1b is a schematic diagram of an MXene @ PU sponge sensor in example 1 of the present invention.
FIG. 2a is a digital graph of sponge dried by dipping for various times in example 1 of the present invention.
FIG. 2b is a graph showing the resistance values of the conductive sponge after being soaked and dried for different times in example 1 of the present invention.
Fig. 3 is a representation of the MXene @ PU sensor L ED lamp in example 1 of the present invention.
Fig. 4 is a bionic mechanism diagram of the sensor in embodiment 1 of the invention.
FIG. 5 is an electron microscope scanning image of the MXene @ PU sensor surface in example 1 of the present invention.
Fig. 6a is a graph of the resistance change of the wearable piezoresistive sensor in human body movement in embodiment 1 of the present invention.
Fig. 6b is a graph showing the sensitivity of the pressure sensor in example 1 of the present invention.
Detailed Description
Specific embodiments of the present invention will be further described below with reference to the following examples and drawings, but the present invention is not limited thereto.
Example 1
(1) Weighing 1g of Ti3C2Dissolving in 80g deionized water, performing ultrasonic treatment for 1h under 70W power of a cell pulverizing ultrasonic machine, transferring into a conical flask after the ultrasonic treatment, soaking polyurethane sponge cut into 12cm in length, 2cm in width and 1cm in thickness into the dispersion liquid in the conical flask, and vacuum pumping and filling for 3 times.
(2) And (2) drying the reaction product prepared in the step (1) in a vacuum oven for 4 hours at the drying temperature of 80 ℃. Obtaining the three-dimensional conductive sponge MXene @ PU. And (4) taking another sponge, repeating the steps for different times, and preparing the three-dimensional conductive sponge which is soaked and dried for different times. FIG. 1a is a schematic diagram of the preparation of MXene @ PU sponge.
(3) And (3) packaging the two ends of the conductive sponge prepared in the step (2) by using copper wires, and connecting the conductive sponge with a detection instrument through silver wires to prepare the piezoresistive sensor. FIG. 1b is a schematic diagram of an MXene @ PU sensor comprising a three-dimensional sponge composite skeleton 1, electrodes 2 and a detection instrument 3; the electrodes 2 are arranged on two sides of the three-dimensional sponge composite framework 1; the detecting instrument 3 is connected with the electrode 2 through a lead 4; the three-dimensional sponge composite framework 1 is filled with transition metal carbide MXene.
FIG. 2a is a digital diagram of the conductive sponge after being dipped and dried for different times, wherein it can be seen that the white sponge gradually darkens with the increase of the dipping times, which shows that MXene is successfully adsorbed on the sponge surface, and the adsorption quantity increases with the increase of the dipping times, FIG. 2b is a resistance value diagram corresponding to the conductive sponge after being dipped and dried for different times, wherein it can be seen that the conductivity of the conductive sponge is improved with the increase of the MXene content, but the resistivity changes little after being dipped and dried for three times, FIG. 3 is a representation of the MXene @ PU sensor L ED lamp, and it can be seen from the brightness of the L ED lamp in the diagram that the MXene PU sensor has better sensing effect.
The spiders can detect very small vibrations in the surrounding environment thanks to their fissured organs in the vicinity of the leg joints between the metatarsal and tarsal bones, as shown in the sensor biomimetic diagram of fig. 4. Small external force changes cause the slits to deform and the neuronal system under the slits can feel. Inspired by the capability, the invention selects the Ti which is a two-dimensional layered material with an accordion structure3C2As a conductive layer. When MXene @ PU sponge is mechanically compressed, the flexing of the PU sponge network causes tension in the MXene conductive layer. Thus, the MXene layer creates mechanical microcracks; when the pressure is released, the microcracks recover. During subsequent pressure sensing, the reversible disconnection-connection of the mechanical microcracks leads to fracture recovery of the partial conductive path, which in turn leads to a corresponding change in conductance. Fig. 5 is an electron microscope scan of the MXene @ PU sensor surface.
In particular, when the edges of the microcracks touch, a certain conductance can be obtained. Once the edge breaks, the conductance begins to drop, exhibiting a response behavior to a strain stimulus. The mechanical micro-crack design mimics the slit geometry of a spider and is expected to yield a highly sensitive sensor to detect ultra-small deformations. However, with further increase in compressive strain, the broken microcracked junction reaches the cracking threshold, showing that conductance no longer decreases with cracking of the crack, benefiting from the massive layer action of MXene, where the major contribution to the conduction path becomes the MXene contact path between the PU backbones, the sensor still maintains a higher sensitivity. Based on the action mechanism, the MXene @ PU sponge sensor can perform multifunctional sensing in a wide strain range and pressure range.
Fig. 6a is a graph of the resistance change of the wearable piezoresistive sensor in human body movement in embodiment 1 of the present invention. Due to the high sensitivity and stability of the piezoresistive sensor, the MXene @ PU sponge is used for detecting human body movement, and the MXene @ PU strain sensor is connected to the wrist by means of the medical adhesive tape.
Fig. 6b is a sensitivity curve of the pressure sensor in example 1 of the present invention. As can be seen from FIG. 4, the working range of the pressure sensor prepared by the embodiment is 0-30KPa, and the sensitivity is 0.001-0.0034KPa-1. These excellent properties indicate the great potential of MXene-based composites as next generation pressure sensors in various applications. In the near future, this simple and effective strategy for manufacturing pressure sensitive materials will further advance towards low cost personal electronic and biomedical devices.
Example 2
(1) Weighing 1g of Ti3C2Dissolving in 80g deionized water, performing ultrasonic treatment for 1h under 70W power of a cell pulverizing ultrasonic machine, transferring into a conical flask after the ultrasonic treatment, soaking polyurethane sponge cut into 12cm in length, 2cm in width and 1cm in thickness into the dispersion liquid in the conical flask, and vacuum pumping and filling for 3 times.
(2) And (2) drying the reaction product prepared in the step (1) in a vacuum oven for 4 hours at the drying temperature of 60 ℃. And repeating dipping and drying for three times to obtain the three-dimensional conductive sponge MXene @ PU.
(3) And (3) packaging the two ends of the conductive sponge prepared in the step (2) by using copper wires, and connecting the conductive sponge with a detection instrument through silver wires to prepare the piezoresistive sensor.
Example 3
(1) Weighing 1g of Ti3C2Dissolving in 80g deionized water, performing ultrasonic treatment for 1h under 70W power of a cell pulverizing ultrasonic machine, transferring into a conical flask after the ultrasonic treatment, soaking polyurethane sponge cut into 12cm in length, 2cm in width and 1cm in thickness into the dispersion liquid in the conical flask, and vacuum pumping and filling for 3 times.
(2) And (2) drying the reaction product prepared in the step (1) in a vacuum oven for 4 hours at the drying temperature of 100 ℃. And repeating dipping and drying for three times to obtain the three-dimensional conductive sponge MXene @ PU.
(3) And (3) packaging the two ends of the conductive sponge prepared in the step (2) by using copper foils, and connecting the conductive sponge with a detection instrument through silver wires to prepare the piezoresistive sensor.
Table 1 range, resistance, and response time of pressure sensors prepared according to embodiments of the present invention.
TABLE 1
As can be seen from table 1, the drying temperature has a large influence on the performance of the sensor, and the conductive filler is partially oxidized due to the excessively high drying temperature, which increases the resistance of the sensor and reduces the conductivity; and due to the fact that the temperature is too low, a relatively obvious micro-crack structure cannot be built on the surface of the three-position framework, and the response time is increased.
Claims (10)
1. A wearable bionic piezoresistive sensor is characterized by comprising a three-dimensional sponge composite framework (1), electrodes (2) and a detection instrument (3); the electrodes (2) are arranged on two sides of the three-dimensional sponge composite framework (1); the detection instrument (3) is connected with the electrode (2) through a lead (4); transition metal carbide MXene is filled in the three-dimensional sponge composite framework (1).
2. The wearable bionic piezoresistive sensor according to claim 1, wherein the transition metal carbide MXene is Ti3C2，Ti2C，Ti4C3，V3C2And V2C, one or more of C.
3. The wearable bionic piezoresistive sensor according to claim 1, wherein the three-dimensional sponge in the three-dimensional sponge composite skeleton is made of polyurethane.
4. The wearable bionic piezoresistive sensor according to claim 1, wherein the material of the electrodes is copper foil or conductive silver paste; the lead is an iron wire, a copper wire or a silver wire.
5. A method of making a wearable biomimetic piezoresistive sensor according to any of claims 1-4, comprising the steps of:
(1) weighing transition metal carbide MXenes, dispersing in water, and performing ultrasonic homogenization to obtain transition metal carbide MXenes dispersion liquid; soaking the three-dimensional sponge in MXene dispersion liquid of transition metal carbide, and vacuumizing and filling to enable the three-dimensional sponge to be filled with MXene;
(2) drying the three-dimensional sponge prepared in the step (1) to obtain a three-dimensional conductive sponge, and marking the three-dimensional conductive sponge as MXene @ PU;
(3) and packaging the two ends of MXene @ PU by using electrode materials, and connecting the electrode materials with a detection instrument through a wire to obtain the wearable bionic piezoresistive sensor.
6. The preparation method according to claim 5, wherein the ultrasound in the step (1) is performed by using a cell crushing ultrasound machine, the power of the ultrasound is 60W-80W, and the time is 1-3 h; the number of times of vacuum pumping and filling is 3-5 times; the mass ratio of the transition metal carbide MXene to water is (1-3) to (70-90).
7. The method according to claim 5, wherein the drying temperature in step (2) is 60-100 ℃ and the drying time is 3-5 h.
8. The preparation method according to claim 5, wherein in the step (2), the soaking and drying process is repeated after the three-dimensional sponge is dried, and the soaking and drying times are 1-5 times.
9. A wearable bionic piezoresistive sensor as claimed in any one of claims 1 to 4, which is used for manufacturing a human body movement detection device.
10. The use of claim 9, wherein said body movements comprise fist making, wrist bending, finger movements and exhalation.
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Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN111982362A (en) * | 2020-08-25 | 2020-11-24 | 工科思维技术(深圳)有限公司 | Method for preparing high-sensitivity flexible piezoresistive sensor based on fracture microstructure |
| CN112113497A (en) * | 2020-08-17 | 2020-12-22 | 华南理工大学 | Self-healing resistance type strain sensor and preparation method and application thereof |
| CN112146795A (en) * | 2020-09-17 | 2020-12-29 | 有研工程技术研究院有限公司 | Preparation method of pressure sensor based on composite sponge porous structure |
| CN112254851A (en) * | 2020-10-16 | 2021-01-22 | 重庆大学 | Alk-Ti3C2Preparation method of PDMS flexible piezoresistive sensor |
| CN112834088A (en) * | 2021-01-21 | 2021-05-25 | 南开大学 | Bionic MXene aerogel-based sensing material and preparation method and application thereof |
| CN113203505A (en) * | 2021-05-14 | 2021-08-03 | 东南大学 | Pressure/strain bimodal sensor based on low-dimensional nano composite material and preparation method thereof |
| CN113235310A (en) * | 2021-05-07 | 2021-08-10 | 北京航空航天大学 | Preparation method and application of piezoresistive sensing fabric |
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| CN113532700A (en) * | 2021-06-24 | 2021-10-22 | 浙江大学 | Flexible pressure sensor with adjustable sensitivity and preparation method and application thereof |
| CN114112124A (en) * | 2021-11-02 | 2022-03-01 | 陕西科技大学 | PEDOT (Poly ethylene glycol Ether phosphate)/PSS (magnesium calcium carbonate)/MgAlV (magnesium aluminium hydroxide)/LDH (layered double hydroxide)/leather flexible wearable sensing material and preparation method thereof |
| CN114486013A (en) * | 2022-02-14 | 2022-05-13 | 东南大学 | Pressure sensor based on capacitance-resistance conversion principle and preparation method thereof |
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| CN112113497A (en) * | 2020-08-17 | 2020-12-22 | 华南理工大学 | Self-healing resistance type strain sensor and preparation method and application thereof |
| CN112113497B (en) * | 2020-08-17 | 2021-12-21 | 华南理工大学 | Self-healing resistance type strain sensor and preparation method and application thereof |
| CN111982362A (en) * | 2020-08-25 | 2020-11-24 | 工科思维技术(深圳)有限公司 | Method for preparing high-sensitivity flexible piezoresistive sensor based on fracture microstructure |
| CN112146795A (en) * | 2020-09-17 | 2020-12-29 | 有研工程技术研究院有限公司 | Preparation method of pressure sensor based on composite sponge porous structure |
| CN112254851A (en) * | 2020-10-16 | 2021-01-22 | 重庆大学 | Alk-Ti3C2Preparation method of PDMS flexible piezoresistive sensor |
| CN112254851B (en) * | 2020-10-16 | 2022-04-22 | 重庆大学 | Alk-Ti3C2Preparation method of PDMS flexible piezoresistive sensor |
| CN112834088A (en) * | 2021-01-21 | 2021-05-25 | 南开大学 | Bionic MXene aerogel-based sensing material and preparation method and application thereof |
| CN113235310B (en) * | 2021-05-07 | 2022-10-11 | 北京航空航天大学 | Preparation method and application of piezoresistive sensing fabric |
| CN113235310A (en) * | 2021-05-07 | 2021-08-10 | 北京航空航天大学 | Preparation method and application of piezoresistive sensing fabric |
| CN113203505A (en) * | 2021-05-14 | 2021-08-03 | 东南大学 | Pressure/strain bimodal sensor based on low-dimensional nano composite material and preparation method thereof |
| CN113418645A (en) * | 2021-06-21 | 2021-09-21 | 重庆邮电大学 | Composite flexible three-dimensional force sensor based on ferromagnetic nanowire/carbon material and preparation method thereof |
| CN113418645B (en) * | 2021-06-21 | 2022-12-27 | 重庆邮电大学 | Composite flexible three-dimensional force sensor based on ferromagnetic nanowire/carbon material and preparation method thereof |
| CN113532700A (en) * | 2021-06-24 | 2021-10-22 | 浙江大学 | Flexible pressure sensor with adjustable sensitivity and preparation method and application thereof |
| CN114112124A (en) * | 2021-11-02 | 2022-03-01 | 陕西科技大学 | PEDOT (Poly ethylene glycol Ether phosphate)/PSS (magnesium calcium carbonate)/MgAlV (magnesium aluminium hydroxide)/LDH (layered double hydroxide)/leather flexible wearable sensing material and preparation method thereof |
| CN114112124B (en) * | 2021-11-02 | 2023-11-10 | 陕西科技大学 | PEDOT (polyethylene glycol terephthalate) PSS/MgAlV-LDH (layered double hydroxide-lateral double hydroxide) leather flexible wearable sensing material and preparation method thereof |
| CN114486013A (en) * | 2022-02-14 | 2022-05-13 | 东南大学 | Pressure sensor based on capacitance-resistance conversion principle and preparation method thereof |
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