CN117367631A - Fiber touch sensor, preparation method and application thereof - Google Patents
Fiber touch sensor, preparation method and application thereof Download PDFInfo
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- CN117367631A CN117367631A CN202311306468.9A CN202311306468A CN117367631A CN 117367631 A CN117367631 A CN 117367631A CN 202311306468 A CN202311306468 A CN 202311306468A CN 117367631 A CN117367631 A CN 117367631A
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Classifications
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- G—PHYSICS
- G06—COMPUTING; CALCULATING OR COUNTING
- G06F—ELECTRIC DIGITAL DATA PROCESSING
- G06F3/00—Input arrangements for transferring data to be processed into a form capable of being handled by the computer; Output arrangements for transferring data from processing unit to output unit, e.g. interface arrangements
- G06F3/01—Input arrangements or combined input and output arrangements for interaction between user and computer
- G06F3/011—Arrangements for interaction with the human body, e.g. for user immersion in virtual reality
-
- 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
- G01L1/14—Measuring force or stress, in general by measuring variations in capacitance or inductance of electrical elements, e.g. by measuring variations of frequency of electrical oscillators
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- Engineering & Computer Science (AREA)
- General Engineering & Computer Science (AREA)
- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- Theoretical Computer Science (AREA)
- Human Computer Interaction (AREA)
- Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
Abstract
The invention provides a fiber touch sensor, a preparation method and application thereof, wherein the fiber touch sensor comprises an STA/MXene/PDA coating fiber electrode layer and an IG/CP fiber electrolyte layer, wherein the STA/MXene/PDA coating fiber electrode layer takes fibers as a substrate, is subjected to hydrophilic modification by a PDA, is loaded with MXene nano-sheets and MXene microspheres, and is subjected to hydrophobic modification by the STA; the IG/CP fiber electrolyte layer takes fiber as a substrate and is loaded with ions and pollen particles with microstructures; the STA/MXene/PDA coating fiber electrode layers are respectively attached to two opposite surfaces of the IG/CP fiber electrolyte layer. The fiber touch sensor has good air permeability, comfort of long-term wearing, good hydrophobicity and self-cleaning performance, and can avoid interference of external liquid or dust in an actual wearing environment so as to keep high-performance sensing.
Description
Technical Field
The invention belongs to the technical field of flexible sensors, and particularly relates to a fiber touch sensor, a preparation method and application thereof.
Background
Flexible tactile sensors have become a critical component of wearable devices in communication with the external environment or the human body. However, conventional flexible tactile sensors are prepared in impermeable polymer films, which, due to their poor breathability, cause inconvenience and discomfort in the application of wearable electronics. In contrast, fiber-based sensors have good breathability and ease of integration with smart apparel. In addition, severe working environments (such as humidity) often lead to reduced performance of the sensing device, and it is important to effectively take waterproof measures to protect the sensing device from other moisture such as sweat secreted from the interior of the skin. Thus, sensors based on fibrous structures have been developed with breathability and hydrophobicity, which are critical to achieving wearable motion detection for human comfort.
Disclosure of Invention
In view of the above, the present invention provides a fiber touch sensor and a preparation method and application thereof, in which a fiber is used as a substrate, and is integrated with a polydopamine PDA with a surface hydrophilically modified, a highly conductive material MXene nanosheet and MXene microsphere, and a super-hydrophobic stearic acid STA to obtain an electrode layer, and a fiber is used as a substrate, and is integrated with an ionic liquid mixed solution containing rich anions and cations and high stability and a pollen particle with a microstructure to obtain an electrolyte layer, so that the prepared sensor has a large number of micropores and micro-channels, provides comfort for long-time wearing, and simultaneously provides the sensor with excellent hydrophobic performance and self-cleaning performance, so that the device can avoid interference of external liquid or dust in an actual wearing environment, and high-performance sensing is maintained.
In order to achieve the above purpose, the technical scheme of the invention is realized as follows:
in one aspect, the present invention provides a fiber optic tactile sensor comprising:
the STA/MXene/PDA coating fiber electrode layer takes fiber as a substrate, is subjected to hydrophilic modification by the PDA, is loaded with MXene nano-sheets and MXene microspheres, and is subjected to hydrophobic modification by the STA to obtain the STA/MXene/PDA coating fiber electrode layer;
the IG/CP fiber electrolyte layer takes fiber as a substrate and is loaded with ions and pollen particles with microstructures;
the STA/MXene/PDA coating fiber electrode layers are respectively attached to two opposite surfaces of the IG/CP fiber electrolyte layer.
In the STA/MXene/PDA coated fiber electrode layer, fibers with good flexibility are adopted to carry out surface hydrophilic treatment in polydopamine solution PDA, then high-conductivity materials MXene nano-sheets and MXene microspheres are added, and by utilizing the effective combination of the MXene nano-sheets and the MXene microspheres, non-woven fabrics fibers can form conductive paths, and the nano-sheet structure and the microsphere structure are beneficial to increasing the contact area between an electrode and an electrolyte layer, so that the performance of the sensor is increased, the original fiber structure of the substrate material is reserved, the excellent conductivity and the micro-nano structure of the substrate material are endowed, and the high-conductivity materials MXene nano-sheets and the MXene microspheres are prevented from being oxidized by the STA with the stearic acid with the hydrophobic performance, and the electrode layer structure and the excellent hydrophobic performance and the self-cleaning performance are endowed;
in the IG/CP fiber electrolyte layer, the fiber with good flexibility is combined with the ionic liquid mixed solution containing rich anions and cations and high stability and the pollen particles with microstructure, so that the electrolyte layer can be ensured to have the micro-nano structure of the pollen particles, and the contact area between the electrode and the electrolyte is effectively increased; in addition, the pollen particles are used as a natural microstructure, have good elasticity and can bear larger mechanical deformation; the pollen particles and the ionic liquid mixed solution are combined and then coated on the surface of the non-woven fabric fiber to form a gel film with air permeability, so that the non-woven fabric fiber is endowed with excellent rebound resilience, and the sensitivity and the detection range of the sensor are improved.
In some preferred embodiments of the fiber touch sensor of the present invention, the STA/MXene/PDA coated fiber electrode layer is prepared by hydrophilic modification of nonwoven fabric fibers in a polydopamine solution, coating an MXene microsphere solution containing MXene nanoplatelets and MXene microspheres, loading the MXene nanoplatelets and MXene microspheres, and then hydrophobic modification with a stearic acid solution.
In some more preferred embodiments of the fibrous tactile sensor of the invention, the mass ratio of Tris-HCl, DA and deionized water in the polydopamine solution is 0.8-2:1.5-2:820-850.
In some more preferred embodiments of the fibrous touch sensor of the present invention, the total mass concentration of the MXene nanoplatelets and the MXene microspheres in the MXene microsphere solution is from 40 to 60wt%.
In some more preferred embodiments of the fibrous tactile sensor of the invention, the mass ratio of STA to water in the stearic acid solution is 0.5-1:100-200.
In some preferred embodiments of the fibrous tactile sensor of the present invention, the IG/CP fibrous electrolyte layer is prepared by coating a mixed solution containing an ionic liquid and pollen particles having a microstructure on the surface of the nonwoven fabric fibers.
In some more preferred embodiments of the fibrous tactile sensor of the invention, the mass ratio of [ EMIM ] [ TFSI ], P (VDF-HFP), DMF, pollen particles in the mixed solution is 12-17:3-7:40-60: 0.7 to 1.2.
In some more preferred embodiments of the fibrous tactile sensor of the invention, the microstructured pollen particles are chrysanthemum pollen particles having conical secondary features.
The invention also provides a preparation method of the fiber touch sensor, which comprises the following steps:
s1, preparing STA/MXene/PDA coating fiber electrode layer
Placing the non-woven fabric fibers into a polydopamine solution for hydrophilic modification, and drying to obtain PDA coating fibers; coating an MXene microsphere solution containing an MXene nanosheet and an Mxene microsphere on one surface of the PDA coating fiber, and drying to obtain the MXene/PDA coating fiber; spraying a stearic acid solution on the surface of the MXene/PDA coating fiber, and drying to obtain the STA/MXene/PDA coating fiber electrode layer;
s2, preparing IG/CP fiber electrolyte layer
Mixing the mixed solution containing the ionic liquid with pollen particles with a microstructure to obtain a uniform IG/CP solution containing the ionic liquid and the pollen particles, coating the IG/CP solution on the surface of non-woven fabric fibers, and drying to obtain the IG/CP fiber electrolyte layer;
and S3, coating IG/CP solution serving as glue on two surfaces of the IG/CP fiber electrolyte layer prepared in the S2, respectively adhering the STA/MXene/PDA coating fiber electrode layers prepared in the S1 on the two surfaces of the IG/CP fiber electrolyte layer, and drying one side, coated with the MXene microsphere solution, of the STA/MXene/PDA coating fiber electrode layers to face the IG/CP fiber electrolyte layer to obtain the fiber touch sensor.
In some preferred embodiments of the method for preparing a fiber touch sensor of the present invention, in the S1, the mass ratio of Tris-HCl, DA and deionized water in the polydopamine solution is 0.8-2:1.5-2:820-850.
In some preferred embodiments of the method for manufacturing a fibrous touch sensor according to the present invention, in S1, the mass concentration of the MXene nanoplatelets and the MXene microspheres in the MXene microsphere solution is 40 to 60wt%.
In some preferred embodiments of the method for manufacturing a fibrous tactile sensor of the present invention, in S1, the mass ratio of STA to water in the stearic acid solution is 0.5 to 1:100 to 200.
In some preferred embodiments of the method of making a fibrous tactile sensor of the invention, in S1, the MXene microsphere solution is prepared by:
dispersing polystyrene microspheres in deionized water, then adding a polydiallyl dimethyl ammonium chloride solution, stirring to obtain positively charged PS microspheres, and removing excessive polydiallyl dimethyl ammonium chloride to obtain positively charged PS microsphere dispersion; and adding the MXene nano-sheets in a stirring state, wherein the self-assembly of static electricity between the MXene nano-sheets and the PS microspheres causes gradual aggregation, then adding the MXene nano-sheets, and then aggregating and dispersing to form the MXene microsphere solution.
In some more preferred embodiments of the method of making fibrous tactile sensors of the invention, the polystyrene microspheres have an average diameter of 0.5 to 3.5 μm; the concentration of the added polydiallyl dimethyl ammonium chloride solution is 0.05 to 0.3 weight percent, and the polydiallyl dimethyl ammonium chloride solution is added into deionized water dispersed with polystyrene microspheres to obtain a mixed solution, wherein the concentration of the polydiallyl dimethyl ammonium chloride in the mixed solution is 0.06 to 0.09 weight percent; removing excessive polydiallyl dimethyl ammonium chloride, and obtaining the PS microsphere with positive electricity, wherein the concentration of the PS microsphere is 3-10 mg/ml; the concentration of the MXene nano-sheets added for the first time is 1-2 mg/ml, after the MXene nano-sheets are added into the mixed solution, the concentration of the MXene nano-sheets in the mixed solution is 3-5 wt%, PS microspheres which are not self-assembled and 20-40 wt% redundant solution are removed, the concentration of the MXene nano-sheets added for the second time is 4-8 mg/ml, and the total mass concentration of the MXene nano-sheets and the MXene microspheres in the MXene microsphere solution is adjusted to be 40-60 wt%.
In some preferred embodiments of the method for preparing a fiber touch sensor of the present invention, in S2, the mass ratio of [ EMIM ] [ TFSI ], P (VDF-HFP), DMF, and pollen particles in the IG/CP solution is 12-17:3-7:40-60: 0.7 to 1.2.
In yet another aspect, the invention provides the use of a fibrous tactile sensor for use in a wearable device. The fiber touch sensor can be used as a sensor unit for monitoring the health state of a human body and detecting the movement of the human body, and can also be used as a sensor array for identifying the spatial pressure distribution of human-computer interaction.
Compared with the prior art, the fiber touch sensor, the preparation method and the application thereof have the following advantages:
(1) The fiber touch sensor starts from three aspects of structural design, material selection and preparation process, and an electrode layer is obtained by integrating a fiber serving as a substrate with polydopamine PDA with surface hydrophilization modification, a high-conductivity material MXene nanosheet and MXene microsphere and super-hydrophobic stearic acid STA; the fiber is used as a substrate, and the electrolyte layer is obtained by integrating the fiber with the ionic liquid mixed solution containing rich anions and cations and high stability and the pollen particles with microstructures, so that the prepared sensor has a large number of micropores and micro-channels, not only has excellent air permeability and provides comfort for long-time wearing, but also endows the sensor with excellent hydrophobic property and self-cleaning property, and the equipment can avoid the interference of external liquid or dust in an actual wearing environment so as to keep high-performance sensing and has high sensitivity;
(2) The STA/MXene/PDA coating fiber electrode layer adopts the fiber with good flexibility to carry out surface hydrophilic treatment in the polydopamine solution PDA, then the high-conductivity material MXene nano-sheet and MXene microsphere are added, the effective combination of the MXene nano-sheet and the MXene microsphere is utilized, the non-woven fabric fiber can form a conductive path, the nano-sheet structure and the microsphere structure are beneficial to increasing the contact area between an electrode and an electrolyte layer, so that the performance of the sensor is increased, the original fiber structure of the substrate material is reserved, the excellent conductivity and the micro-nano structure of the substrate material are provided, the high-conductivity material MXene nano-sheet and the MXene microsphere are prevented from being oxidized by the hydrophobic modification of stearic acid with the hydrophobic performance, and the electrode layer structure and the excellent hydrophobic performance and the self-cleaning performance are provided;
(3) In the IG/CP fiber electrolyte layer, the fiber with good flexibility is combined with the ionic liquid mixed solution containing rich anions and cations and high stability and the pollen particles with microstructure, so that the electrolyte layer can be ensured to have the micro-nano structure of the pollen particles, and the contact area between the electrode and the electrolyte is effectively increased; in addition, the pollen particles are used as a natural microstructure, have good elasticity and can bear larger mechanical deformation; the pollen particles and the ionic liquid mixed solution are combined and then coated on the surface of the non-woven fabric fiber to form a gel film with air permeability, so that the non-woven fabric fiber is endowed with excellent rebound resilience, and the sensitivity and the detection range of the sensor are improved.
Drawings
FIG. 1 is a schematic diagram of a fiber optic tactile sensor according to the present invention;
FIG. 2 is a schematic diagram of the working principle of the fiber tactile sensor according to the present invention;
FIG. 3 is a schematic view of the preparation process of the STA/MXene/PDA coated fiber electrode layer in example 1 of the present invention;
FIG. 4 is a schematic view showing the preparation process of the IG/CP fiber electrolyte layer in example 1 of the present invention;
in fig. 5, fig. 5a is a cross-sectional electron microscopy of a fibre sensor unit; FIG. 5b is a fiber electron microscope image of the PDA coating; FIG. 5c is an electron microscope image of an MXene nanoplatelet and an MXene microsphere; fig. 5d is an electron microscope image of the STA flit; FIG. 5e is an electron microscope image of chrysanthemum pollen;
FIG. 6a is a graph of sensor response time detection; FIG. 6b is a graph of sensor dynamic pressure performance; FIG. 6c is a sensor minimum detection limit diagram; FIG. 6d is a sensor stability diagram;
FIG. 7 is a schematic illustration of a flexible display of a fiber optic tactile sensor according to the present invention;
FIG. 8 is a schematic diagram of the breathability of a fibrous tactile sensor according to the present invention;
FIG. 9 is a schematic representation of the hydrophobicity display of a fiber tactile sensor according to the present invention;
FIG. 10 is a schematic illustration of a self-cleaning display of a fiber tactile sensor according to the present invention;
FIG. 11 is a schematic diagram of an application of the fiber optic tactile sensor according to the present invention, wherein FIG. 11a is a respiratory signal monitoring diagram; FIG. 11b is a pulse signal monitoring diagram; FIG. 11c is a view of wrist bending motion detection; FIG. 11d is a finger bending motion detection diagram; FIG. 11e is a knee flexion motion detection graph; FIG. 11f is an elbow bend detection diagram; FIG. 11g is a pictorial view of a sensor array; FIG. 11h is a diagram of three legume entities placed on a sensor array of different weights; FIG. 11i is a graph of pressure profiles identifying three different weight beans on a sensing array; FIG. 11j is a pictorial view of the sensor array sewn to the glove; FIG. 11k is a physical diagram of an apple being grasped by wearing a glove; fig. 11l is a two-dimensional spatial pressure profile of an apple being grasped by a glove.
Description of the reference numerals
1-IG/CP fibrous electrolyte layer; 2-STA/MXene/PDA coated fiber electrode layer; 3-pollen particles having a microstructure; 4-MXene nanoplatelets; 5-MXene microspheres; 6-STA flits.
Detailed Description
Unless defined otherwise, technical terms used in the following examples have the same meaning as commonly understood by one of ordinary skill in the art to which the present invention pertains. The test reagents used in the following examples, unless otherwise specified, are all conventional biochemical reagents; the experimental methods are conventional methods unless otherwise specified.
The present invention will be described in detail with reference to the following examples and drawings.
A method for manufacturing a fiber tactile sensor, comprising the steps of:
s1, preparing STA/MXene/PDA coating fiber electrode layer
Placing the non-woven fabric fiber into a polydopamine PDA solution (the mass ratio of Tris-HCl to DA to deionized water in the polydopamine solution is 0.8-2:1.5-2:820-850) for surface hydrophilic modification treatment, and drying to obtain the PDA coated fiber; coating an MXene microsphere solution (the MXene microsphere solution contains MXene nanosheets and MXene microspheres, the mass concentration of the MXene nanosheets and the MXene microspheres is 40-60 wt%) on one side of the PDA coating fiber, and drying to obtain the MXene/PDA coating fiber; spraying a solution of STA (stearic acid) on the surface of the MXene/PDA coating fiber, wherein the mass ratio of STA to water in the solution of STA to water is 0.5-1:100-200, and drying to obtain the STA/MXene/PDA coating fiber electrode layer;
wherein the MXene microsphere solution is prepared by:
dispersing Polystyrene (PS) microspheres with the average diameter of 0.5-3.5 mu m in deionized water to obtain PS microsphere dispersion with the concentration of 2-6wt%; then adding 0.05-0.3 wt% polydiallyl dimethyl ammonium chloride (PDDA) solution into PS microsphere dispersion liquid to obtain mixed liquid with polydiallyl dimethyl ammonium chloride concentration of 0.06-0.09 wt%, stirring to obtain positively charged PS microsphere, and removing excessive polydiallyl dimethyl ammonium chloride to obtain positively charged PS microsphere dispersion (3-10 mg/ml); adding low-concentration MXene nano-sheets (1-2 mg/ml) into the positively charged PS microsphere dispersion under the stirring state to obtain mixed solution with the concentration of 3-5wt% of MXene nano-sheets, gradually aggregating due to electrostatic self-assembly between the MXene nano-sheets and the PS microsphere, removing the non-self-assembled PS microsphere and 20-40wt% of redundant solution, then adding high-concentration MXene nano-sheets (4-8 mg/ml), adjusting the total mass concentration of the MXene nano-sheets and the MXene microsphere in the MXene microsphere solution to 40-60wt%, and further aggregating and dispersing under mild ultrasonic treatment to form the MXene microsphere solution.
S2, preparing IG/CP fiber electrolyte layer
Pretreatment of pollen particles with microstructure: placing the aggregated pollen particles in ethanol, centrifuging, washing the pollen particles with ethanol by ultrasonic vibration for several times, filtering, and drying the wet pollen particles;
preparation of IG/CP solution: preparing [ EMIM ] [ TFSI ], P (VDF-HFP) and DMF according to the mass ratio of 12-17:3-7:40-60, and obtaining a mixed solution (IG solution) containing ionic liquid after polymer particles are completely dissolved; adding the pretreated pollen particles into an IG solution to obtain a uniform IG/CP solution containing ionic liquid and pollen particles ([ EMIM ] [ TFSI ], P (VDF-HFP), DMF and pollen particles with the mass ratio of 12-17:3-7:40-60:0.7-1.2), coating the IG/CP solution on the surface of non-woven fabric fibers, and drying to obtain the IG/CP fiber electrolyte layer;
and S3, coating IG/CP solution serving as glue on two surfaces of the IG/CP fiber electrolyte layer prepared in the S2, respectively adhering the STA/MXene/PDA coating fiber electrode layers prepared in the S1 on the two surfaces of the IG/CP fiber electrolyte layer, and drying one side, coated with the MXene nano-sheets and the MXene microsphere solution, of the STA/MXene/PDA coating fiber electrode layers towards the IG/CP fiber electrolyte layer to obtain the fiber touch sensor.
As shown in FIG. 1, the fiber touch sensor comprises an IG/CP fiber electrolyte layer 1 arranged in an intermediate layer and a sensor body arranged on the intermediate layerISTA/MXene/PDA coating fiber electrode layer 2 on one side of G/CP fiber electrolyte layer 1 and provided onIA STA/MXene/PDA coating fiber electrode layer 2 on the other side of the G/CP fiber electrolyte layer; the IG/CP fiber electrolyte layer 1 takes fiber as a substrate and is loaded with ions and pollen particles 3 with microstructures; the STA/MXene/PDA coated fiber electrode layer 2 takes fiber as a substrate, is subjected to hydrophilic modification by PDA, is loaded with MXene nano-sheets 4 and MXene microspheres 5, and is subjected to hydrophobic modification by STA, and is then loaded with STA micro-sheets 6.
As shown in fig. 2, the fiber touch sensor works according to the following principle: when pressure is applied to the fiber sensor, the STA/MXene/PDA coating fiber electrode layer and the IG/CP fiber electrolyte layer of the sensor deform under the action of the pressure, so that the contact area between the electrolyte layer and the electrode layer is enlarged, the distance is reduced, and the capacitance is increased; when the external pressure disappears, the STA/MXene/PDA coating fiber electrode layer and the IG/CP fiber electrolyte layer can be restored to the original state, and the capacitance can be restored to the original value; the change of the capacitance can be converted into an electric signal and transmitted to a subsequent processing circuit, so that the force is monitored;
when the electrode layer contacts with the electrolyte layer, under the action of an external power supply, the internal surface charges of the STA/MXene/PDA coating fiber electrode adsorb ions from the IG/CP fiber electrolyte, and the ions respectively form interface layers with the same charge quantity and opposite sign with the charge quantity of the internal surface of the STA/MXene/PDA coating fiber electrode at two sides of the IG/CP fiber electrolyte interface, and due to the potential difference on the electrode/electrolyte interface, the two layers of charges can not cross the boundary and neutralize each other, so that the super capacitor with stable structure is formed.
Example 1
A fiber tactile sensor is prepared comprising the steps of:
(1) Preparation of STA/MXene/PDA coated fiber electrode layer (as shown in FIG. 3)
Adding Tris-HCl, 4- (2-amino ethyl) benzene-1,2-Diol (DA) and deionized water into a beaker according to a mass ratio of 1:1.7:834, stirring for 10 minutes in a magnetic stirrer water bath kettle at 20 ℃, then placing non-woven fabrics into the beaker, soaking for 4-6 hours, taking out, repeatedly flushing with deionized water, and drying in an oven at 70 ℃ for 20 minutes to obtain PDA coated fibers;
dispersing Polystyrene (PS) microspheres with the average diameter of 3 mu m in deionized water, then adding polydiallyl dimethyl ammonium chloride (PDDA) solution with the concentration of 0.1wt% to obtain mixed solution with the concentration of polydiallyl dimethyl ammonium chloride of 0.08wt%, stirring for 12 hours to obtain positively charged PS microspheres, and centrifuging to remove excessive polydiallyl dimethyl ammonium chloride to obtain positively charged PS microsphere dispersion (3 mg/ml); adding MXene nano-sheets with the concentration of 1mg/ml under the stirring state to obtain a mixed solution with the concentration of 3wt% of MXene nano-sheets, gradually aggregating due to electrostatic self-assembly between the MXene nano-sheets and PS microspheres, removing the PS microspheres which are not self-assembled and 40wt% of redundant solution, adding MXene nano-sheets with the concentration of 5mg/ml, adjusting the total mass concentration of the MXene nano-sheets and the MXene microspheres in the MXene microsphere solution to be 50wt%, and further aggregating and dispersing under mild ultrasonic treatment to form the MXene microsphere solution with the concentration; coating the MXene microsphere solution on one surface of the PDA coating fiber, and drying in an oven at 70 ℃ for 20 minutes to obtain the MXene/PDA coating fiber;
adding stearic acid (STA) and hot water into a beaker according to the mass ratio of 1:200, placing the beaker into a water bath kettle of a magnetic stirrer at 1000rpm at 70 ℃ for stirring for 1 hour to obtain a solution of the STA stearate, spraying the solution of the STA stearate onto the surface of the MXene/PDA coated fiber, and drying the solution of the STA stearate in an oven at 70 ℃ for 20 minutes to obtain an STA/MXene/PDA coated fiber electrode layer;
(2) Preparation of IG/CP fibrous electrolyte layer (as shown in FIG. 4)
Pretreatment is carried out on chrysanthemum pollen particles: placing the gathered chrysanthemum pollen particles in ethanol, magnetically stirring for 4 hours, centrifuging, washing the pollen particles with ethanol by ultrasonic vibration for several times, filtering with filter paper, and drying the wet pollen in an oven at 60 ℃ for 1 hour;
preparation of IG/CP solution: placing [ EMIM ] [ TFSI ], P (VDF-HFP) and DMF in a mass ratio of 12:5:50 into a beaker, sealing the mouth of the beaker by using a preservative film to prevent possible evaporation and exchange with external substances, and stirring the mixture solution in a 50 ℃ magnetic stirrer water bath kettle for 3 hours until the solution becomes transparent, wherein polymer particles are completely dissolved to obtain an IG solution; adding the pretreated pollen particles into an IG solution, and keeping magnetic stirring at 500rpm for 30 minutes to obtain a uniform IG/CP solution containing ionic liquid and pollen particles ([ EMIM ] [ TFSI ], P (VDF-HFP), DMF and pollen particles with the mass ratio of 12:5:50:1);
completely soaking non-woven fabrics in an IG/CP solution, taking out, and drying in an oven at 60 ℃ for 40 minutes to obtain an IG/CP fiber electrolyte layer;
(3) And coating a small amount of IG/CP solution on two surfaces of the prepared IG/CP fiber electrolyte layer to serve as glue, adhering the prepared STA/MXene/PDA coating fiber electrode layers on the two surfaces of the IG/CP fiber electrolyte layer respectively, enabling one side of the STA/MXene/PDA coating fiber electrode layers coated with the MXene microsphere solution to face the IG/CP fiber electrolyte layer, and drying in an oven at 50 ℃ for 20 minutes after adhesion to obtain the fiber touch sensor.
Example 2
On the basis of example 1, the difference from example 1 is that when an IG/CP fibrous electrolyte layer is prepared, the content of ionic liquid is different, and [ EMIM ] [ TFSI ], P (VDF-HFP) and DMF are prepared according to the mass ratio of 15:5:50.
Example 3
On the basis of example 1, the difference from example 1 is that when an IG/CP fibrous electrolyte layer is prepared, the content of ionic liquid is different, and [ EMIM ] [ TFSI ], P (VDF-HFP) and DMF are prepared according to the mass ratio of 17:5:50.
Example 4
On the basis of example 2, the addition amount of pollen particles was different when preparing the IG/CP fibrous electrolyte layer, and the mass ratio of [ EMIM ] [ TFSI ], P (VDF-HFP), DMF, pollen particles was 15:5:50:0.7.
Example 5
On the basis of example 2, the addition amount of pollen particles was different when preparing the IG/CP fibrous electrolyte layer, and the mass ratio of [ EMIM ] [ TFSI ], P (VDF-HFP), DMF, and pollen particles was 15:5:50:1.2.
Comparative example 1
On the basis of example 1, the difference from example 1 is that when an IG/CP fibrous electrolyte layer is prepared, the content of ionic liquid is different, and [ EMIM ] [ TFSI ], P (VDF-HFP) and DMF are prepared according to the mass ratio of 5:5:50.
Comparative example 2
On the basis of example 1, the difference from example 1 is that when an IG/CP fibrous electrolyte layer is prepared, the content of ionic liquid is different, and [ EMIM ] [ TFSI ], P (VDF-HFP) and DMF are prepared according to the mass ratio of 10:5:50.
Comparative example 3
On the basis of example 1, the difference from example 1 is that when an IG/CP fibrous electrolyte layer is prepared, the content of ionic liquid is different, and [ EMIM ] [ TFSI ], P (VDF-HFP) and DMF are prepared according to the mass ratio of 18:5:50.
Comparative example 4
On the basis of example 2, the addition amount of pollen particles was different when preparing the IG/CP fibrous electrolyte layer, and the mass ratio of [ EMIM ] [ TFSI ], P (VDF-HFP), DMF, and pollen particles was 15:5:50:0, which was different from example 2.
Comparative example 5
On the basis of example 2, the addition amount of pollen particles was different when preparing the IG/CP fibrous electrolyte layer, and the mass ratio of [ EMIM ] [ TFSI ], P (VDF-HFP), DMF, and pollen particles was 15:5:50:2.
Sensitivity tests were performed on examples 1-3 and comparative examples 1-3 to investigate the effect of varying ionic liquid content in the IG/CP fibrous electrolyte layer on the sensitivity of the prepared fibrous tactile sensor, and the data are shown in table 1.
TABLE 1
As can be seen from table 1, when the ratio of P (VDF-HFP)/DMF/CP is determined to be 5:50:1, it is shown that the ionic liquid content of different ratios in the IG/CP fibrous electrolyte layer affects the performance of the sensor; with the increase of the content of the ionic liquid, the performance of the sensor is gradually improved. However, when the content of the ionic liquid is too large, the phenomenon of liquid outflow of the IG/CP fibrous electrolyte occurs, that is, when the content ratio of the ionic liquid exceeds 17, the fibrous electrolyte having a gas-permeable solid film cannot be formed. Therefore, the optimal ionic liquid proportion is 12-17.
Sensitivity tests were performed on examples 2, 4, and 5 and comparative examples 4 and 5, and the effect of different amounts of pollen particles added to the IG/CP fibrous electrolyte layer on the sensitivity of the prepared fibrous tactile sensor was studied, and the data are shown in table 2.
TABLE 2
As can be seen from table 2, when the ratio of [ EMIM ] [ TFSI ]/P (VDF-HFP)/DMF is determined to be 15:5:50, it is shown that the introduction of chrysanthemum pollen with conical secondary characteristics into the IG/CP fiber electrolyte layer can improve the performance (such as sensitivity, detection range) of the sensor; however, when the pollen content is too high, the aggregation of pollen particles is caused, that is, more than 1.2, thereby destroying the coarse microstructure in the IG/CP fibrous electrolyte layer, resulting in the degradation of the sensor performance, the optimum pollen content ratio is determined to be 0.7-1.2.
Performance testing of prepared fiber touch sensor
1. As shown in fig. 5, each layer of the fiber touch sensor prepared by the method is clearly visible (fig. 5a is a cross-sectional electron microscope view of the fiber sensor unit); the structure and the morphology of the original fiber are still maintained for the PDA coating fiber subjected to the polydopamine PDA modification treatment (FIG. 5b is an electron microscope image of the PDA coating fiber); after that, the sensitivity of the sensor can be improved by introducing a high-conductivity material MXene nano lamellar structure and a MXene microsphere structure (FIG. 5c is an electron microscope image of the MXene nano lamellar and the MXene microsphere); the super-hydrophobic STA sheet structure in the STA/MXene/PDA coating fiber can endow the sensor with excellent hydrophobicity (FIG. 5d is an electron microscope image of the STA microchip); the IG/CP fiber electrolyte layer is introduced with a chrysanthemum pollen structure with conical secondary characteristics (figure 5e is an electron microscope image of the chrysanthemum pollen); therefore, in the process of applying pressure to the fiber touch sensor, the unique microstructure of the fiber touch sensor can remarkably increase the contact area between the IG/CP fiber electrolyte and the STA/MXene/PDA coating fiber electrode, so that the sensitivity of the sensor is effectively improved.
2. As shown in fig. 6, taking the fiber touch sensor prepared in example 2 as an example, the fiber touch sensor has an ultrafast response time of 50ms (fig. 6a is a sensor response time detection chart); has good dynamic sensing performance (FIG. 6b is a graph of sensor dynamic pressure performance); has an ultra-low detection limit of 45Pa (FIG. 6c is a sensor minimum detection limit diagram); has excellent stability, and the reciprocating experiment has no error basically (fig. 6d is a sensor stability diagram).
3. As shown in FIG. 7, the fiber touch sensor prepared by the invention has excellent flexibility and can be bent, folded in half and twisted.
4. As shown in FIG. 8, the STA/MXene/PDA coating fiber electrode layer (marked as electrode in the figure), the IG/CP fiber electrolyte layer (marked as electrolyte in the figure) and the fiber touch sensor (marked as sensor in the figure) prepared by the invention have good air permeability, and the air permeability of the fiber touch sensor is about 224.9mm/s, more than 6 times of the TPU film and more than 3 times of the nylon.
5. As shown in fig. 9, the fiber touch sensor prepared by the invention has good hydrophobicity, and the contact angle between the artificial sweat and the fiber sensor is 151.9 degrees.
6. As shown in FIG. 10, the fiber touch sensor prepared by the invention has good self-cleaning property, and the flour and pollen on the surface of the fiber sensor are washed by water, so that the fiber touch sensor can slide down quickly along with water drops.
7. As shown in fig. 11, the flexible, breathable, waterproof and self-cleaning fiber sensor prepared by the invention can be used as a sensor unit for actual human health status monitoring and motion detection (fig. 11a is a respiratory signal monitoring diagram, fig. 11b is a pulse signal monitoring diagram, fig. 11c is a wrist bending motion detecting diagram, fig. 11d is a finger bending motion detecting diagram, fig. 11e is a knee bending motion detecting diagram, fig. 11f is an elbow bending motion detecting diagram), and can also be used as a sensor array for identifying spatial pressure distribution of human-computer interaction (fig. 11g is a physical diagram of the sensor array, fig. 11h is a physical diagram of three beans placed on the sensor array, fig. 11i is a physical diagram for identifying three beans with different weights on the sensor array, fig. 11j is a physical diagram of the sensor array sewn on a glove, fig. 11k is a physical diagram of an apple being worn by a glove grasping, and fig. 11l is a two-dimensional spatial pressure distribution of an apple being worn by a glove grasping).
The fiber sensor prepared by the invention has good air permeability and long-term wearing comfort, and also has good hydrophobicity and self-cleaning performance. The air permeability and the comfort can enable the fiber sensor to perform long-time contact work on the premise of not damaging the skin of a human body; the hydrophobicity can prevent other moisture such as human sweat from entering the inside of the fiber sensor, and the service life of the sensor and the accuracy and stability of signal monitoring are affected; the self-cleaning performance can reduce damage to the sensor surface material, and effectively remove pollutants such as impurities on the sensor surface.
The foregoing description of the preferred embodiments of the invention is not intended to be limiting, but rather is intended to cover all modifications, equivalents, alternatives, and improvements that fall within the spirit and scope of the invention.
Claims (10)
1. A fiber optic tactile sensor, comprising:
the STA/MXene/PDA coating fiber electrode layer takes fiber as a substrate, is subjected to hydrophilic modification by the PDA, is loaded with MXene nano-sheets and MXene microspheres, and is subjected to hydrophobic modification by the STA to obtain the STA/MXene/PDA coating fiber electrode layer;
the IG/CP fiber electrolyte layer takes fiber as a substrate and is loaded with ions and pollen particles with microstructures;
the STA/MXene/PDA coating fiber electrode layers are respectively attached to two opposite surfaces of the IG/CP fiber electrolyte layer.
2. The fiber optic tactile sensor according to claim 1, wherein: the STA/MXene/PDA coated fiber electrode layer is prepared by hydrophilic modification of non-woven fabrics fibers in a polydopamine solution, coating of an MXene microsphere solution containing an MXene nano-sheet and an Mxene microsphere, loading of the MXene nano-sheet and the MXene microsphere, and hydrophobic modification of a stearic acid solution.
3. The fiber optic tactile sensor according to claim 2, wherein: the mass ratio of Tris-HCl to DA to deionized water in the polydopamine solution is 0.8-2:1.5-2:820-850;
the total mass concentration of the MXene nano-sheets and the MXene microspheres in the MXene microsphere solution is 40-60 wt%;
the mass ratio of the STA to the water in the stearic acid solution is 0.5-1:100-200.
4. The fiber optic tactile sensor according to claim 1, wherein: the IG/CP fiber electrolyte layer is prepared by coating a mixed solution containing ionic liquid and pollen particles with microstructures on the surface of non-woven fabric fibers.
5. The fiber optic tactile sensor according to claim 4, wherein: the mass ratio of [ EMIM ] [ TFSI ], P (VDF-HFP), DMF and pollen particles in the mixed solution is 12-17:3-7:40-60: 0.7 to 1.2.
6. The fiber optic tactile sensor according to claim 4, wherein: the pollen particles with the microstructure are chrysanthemum pollen particles with conical secondary characteristics.
7. A method for manufacturing a fiber tactile sensor, comprising the steps of:
s1, preparing STA/MXene/PDA coating fiber electrode layer
Placing the non-woven fabric fibers into a polydopamine solution for hydrophilic modification, and drying to obtain PDA coating fibers; coating an MXene microsphere solution containing an MXene nanosheet and an Mxene microsphere on one surface of the PDA coating fiber, and drying to obtain the MXene/PDA coating fiber; spraying a stearic acid solution on the surface of the MXene/PDA coating fiber, and drying to obtain the STA/MXene/PDA coating fiber electrode layer;
s2, preparing IG/CP fiber electrolyte layer
Mixing the mixed solution containing the ionic liquid with pollen particles with a microstructure to obtain a uniform IG/CP solution containing the ionic liquid and the pollen particles, coating the IG/CP solution on the surface of non-woven fabric fibers, and drying to obtain the IG/CP fiber electrolyte layer;
and S3, coating IG/CP solution serving as glue on two surfaces of the IG/CP fiber electrolyte layer prepared in the S2, respectively adhering the STA/MXene/PDA coating fiber electrode layers prepared in the S1 on the two surfaces of the IG/CP fiber electrolyte layer, and drying one side, coated with the MXene microsphere solution, of the STA/MXene/PDA coating fiber electrode layers to face the IG/CP fiber electrolyte layer to obtain the fiber touch sensor.
8. The method of manufacturing a fiber optic tactile sensor according to claim 7, wherein: in the S1, the mass ratio of Tris-HCl to DA to deionized water in the polydopamine solution is 0.8-2:1.5-2:820-850; the total mass concentration of the MXene nano-sheet and the MXene microsphere in the MXene microsphere solution is 40-60 wt%; the mass ratio of the STA to the water in the stearic acid solution is 0.5-1:100-200;
preferably, in the S2, the mass ratio of [ EMIM ] [ TFSI ], P (VDF-HFP), DMF and pollen particles in the IG/CP solution is 12-17: 3-7:40-60: 0.7 to 1.2.
9. The method of manufacturing a fiber optic tactile sensor according to claim 7, wherein: in S1, the MXene microsphere solution was prepared by:
dispersing polystyrene microspheres in deionized water, then adding a polydiallyl dimethyl ammonium chloride solution, stirring to obtain positively charged PS microspheres, and removing excessive polydiallyl dimethyl ammonium chloride to obtain positively charged PS microsphere dispersion; adding an MXene nano-sheet in a stirring state, gradually aggregating due to electrostatic self-assembly between the MXene nano-sheet and the PS microsphere, then adding the MXene nano-sheet, and aggregating and dispersing to form an MXene microsphere solution;
preferably, the polystyrene microspheres have an average diameter of 0.5 to 3.5 μm; the concentration of the added polydiallyl dimethyl ammonium chloride solution is 0.05 to 0.3 weight percent, and the polydiallyl dimethyl ammonium chloride solution is added into deionized water dispersed with polystyrene microspheres to obtain a mixed solution, wherein the concentration of the polydiallyl dimethyl ammonium chloride in the mixed solution is 0.06 to 0.09 weight percent; removing excessive polydiallyl dimethyl ammonium chloride, and obtaining the PS microsphere with positive electricity, wherein the concentration of the PS microsphere is 3-10 mg/ml; the concentration of the MXene nano-sheets added for the first time is 1-2 mg/ml, after the MXene nano-sheets are added into the mixed solution, the concentration of the MXene nano-sheets in the mixed solution is 3-5 wt%, PS microspheres which are not self-assembled and 20-40 wt% redundant solution are removed, the concentration of the MXene nano-sheets added for the second time is 4-8 mg/ml, and the total mass concentration of the MXene nano-sheets and the MXene microspheres in the MXene microsphere solution is adjusted to be 40-60 wt%.
10. Use of the fibrous tactile sensor according to any one of claims 1 to 6 or prepared by the preparation method according to any one of claims 7 to 9, characterized in that: the application of the fiber touch sensor in a wearable device.
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