CN111504520B - Integrated flexible stretchable touch sensor based on super-capacitor sensing principle - Google Patents
Integrated flexible stretchable touch sensor based on super-capacitor sensing principle Download PDFInfo
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- CN111504520B CN111504520B CN202010310831.4A CN202010310831A CN111504520B CN 111504520 B CN111504520 B CN 111504520B CN 202010310831 A CN202010310831 A CN 202010310831A CN 111504520 B CN111504520 B CN 111504520B
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- 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
- G01L1/142—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 using capacitors
Abstract
The invention provides an integrated flexible stretchable touch sensor based on a super-capacitor sensing principle, which comprises a foam upper electrode layer, a foam electrolyte layer and a foam lower electrode layer which are sequentially arranged, wherein the foam electrolyte layer is prepared by foaming a mixture comprising a solvent, a high polymer material, esters, an ionophore and bacterial cellulose, and the mass ratio of the five materials is (25-30): (3-4): (4-6) and (1-2) to (0.4-0.6), wherein the foam upper electrode layer and the foam lower electrode layer are made of the same material and are prepared by foaming a mixture comprising a solvent, a high polymer material, esters, a conductive material and bacterial cellulose, and the mass ratio of the five materials is (25-30) to (3-4): (4-6):(3-4):(0.4-0.6). The sensor has the characteristic of integral structure of the device, the combination between the electrode and the electrolyte is good, no microcosmic physical gap exists, and the sensor has the advantages of ultrahigh flexibility and stretchability while obtaining high sensitivity and wide detection range based on the super-capacitor principle.
Description
Technical Field
The invention belongs to the technical field of flexible sensors, and particularly relates to an integrated flexible stretchable touch sensor based on a super-capacitor sensing principle.
Background
The flexible, wearable, flexible and humanized development of the soft electronic equipment has important significance for meeting the increasing requirements of complexity and multiple functions of modern electronic products of people. Strain sensors can produce repeatable electrical changes when subjected to mechanical deformation and have wide application in robotic, athletic, health monitoring and therapeutic fields. At present, the sensor has defects in material performance and device structure in terms of flexibility and stretchability development. Some representative strain sensors that have been proposed so far use conductive materials such as carbon nanotubes, metals/semiconductors, graphene, and conductive polymers as electrode materials, and the electrodes are made flexible by combining the conductive materials with an elastomer substrate. . However, electrodes obtained by adhesively bonding a conductive layer to a substrate layer have limited stretch properties, typically less than 200%. For the whole sensing device, it is usually obtained by attaching and combining separately prepared electrode layers and sensing function layers (e.g. dielectric layers, piezoelectric layers). Because the parts of the device are not integrally organically combined, the parts are easy to split or even separate during the flexible bending and repeated stretching use process. The limited flexibility and stretching degree cause the defects of small measurement factor, small measurement range, low sensitivity, poor long-term repeatability and the like of the sensor.
Disclosure of Invention
Aiming at the problems in the field, the invention provides a touch sensor with an integrated device integral structure, wherein an electrode layer and an electrolyte layer are combined into a unified body based on the same network substrate material, and different functions of electrode conduction and ion conduction are realized by adding different functional materials in the touch sensor. In addition, the sensor is based on a super-capacitor sensing principle, and has the advantages of being high in sensitivity, wide in detection range, ultra-high in flexibility and stretchable.
In order to achieve the purpose, the technical scheme of the invention is realized as follows:
an integrated flexible stretchable touch sensor based on a super-capacitor sensing principle comprises a foam upper electrode layer, a foam electrolyte layer and a foam lower electrode layer which are sequentially arranged, wherein the foam electrolyte layer is prepared by foaming a mixture comprising a solvent, a high polymer material, esters, an ionophore and bacterial cellulose, and the mass ratio of the five materials is (25-30) to (3-4): (4-6) and (1-2) to (0.4-0.6), wherein the foam upper electrode layer and the foam lower electrode layer are made of the same material and are prepared by foaming a mixture comprising a solvent, a high polymer material, esters, a conductive material and bacterial cellulose, and the mass ratio of the five materials is (25-30) to (3-4): (4-6):(3-4):(0.4-0.6).
Preferably, the solvent is water or an ionic liquid, wherein the ionic liquid is a salt that is liquid at or near room temperature and is composed entirely of organic cations including, but not limited to, quaternary ammonium ions, quaternary phosphonium ions, imidazolium ions, and pyrrolide ions, and inorganic or organic anions including, but not limited to, halogen ions, tetrafluoroborate ions, and hexafluorophosphate ions.
Preferably, the polymer material includes, but is not limited to, polyvinyl alcohol (PVA), thermoplastic polyurethane elastomer (TPU), or polystyrene (EPS).
Preferably, the esters include, but are not limited to, Propylene Carbonate (PC), Ethylene Carbonate (EC), Ethyl Methyl Carbonate (EMC), dimethyl carbonate (DMC), ethylene carbonate (DEC), or a mixture of two or more thereof.
Preferably, the ionic carrier is one or a mixture of more than two of acid, alkali and salt, preferably one or a mixture of more than two of sulfuric acid, phosphoric acid, sodium hydroxide, potassium hydroxide, sodium sulfate and sodium bicarbonate.
The bacterial cellulose is a porous netted nano-scale biopolymer synthesized by microbial fermentation, can enhance the tensile resistance of an electrode and an electrolyte, and has the following principle: hydrogen bonds between the bacterial cellulose and the polyvinyl alcohol form a double-net structure, and stress can be transferred at the fastest speed.
Preferably, the conductive material is metal, carbon or conductive polymer, including but not limited to copper, aluminum, gold, silver, nickel, graphite, acetylene black, carbon nanotube, graphene, MXene, polypyrrole, polythiophene, or a composite of two or more thereof.
Preferably, the thickness of the foam upper electrode layer and the foam lower electrode layer is smaller than that of the foam electrolyte layer.
Preferably, the shape of the flexible stretchable tactile sensor includes, but is not limited to, a rectangular parallelepiped, a cylinder, a triangular pyramid.
Preferably, both ends of the foam upper electrode layer and the foam lower electrode layer are electrically connected with the outside through pasting conductive metal wires by using silver paste.
Preferably, the upper surface of the foam upper electrode layer and the lower surface of the foam lower electrode layer are covered with polymer films as packaging layers. The encapsulation layer is preferably a PVA film. The packaging layer is required to be as thin and flexible as possible, and the packaging layer is selected from materials including but not limited to PVA film.
The invention also provides a preparation method of the integrated flexible stretchable touch sensor based on the super-capacitor sensing principle, which specifically comprises the following steps:
(1) preparation of foam bottom electrode layer
Mixing water, bacterial cellulose and a high polymer material, adding an ionophore, heating for 1-2 hours at 80-100 ℃, cooling to 75 ℃ after the high polymer material is completely dissolved, adding an emulsifier and esters, stirring for reaction for 2.5 hours, adding graphene, stirring to a uniform state, cooling to 35 ℃, adding a foaming agent, quickly stirring uniformly, pouring into a mold, and putting into a refrigerator to freeze until the mixture is solidified to serve as a lower electrode layer of foam;
(2) Preparation of foamed electrolyte layer
Mixing water, bacterial cellulose and a high polymer material, adding an ionophore, heating for 1-2 hours at 80-100 ℃, cooling to 75 ℃ after the high polymer material is completely dissolved, adding an emulsifier and esters, stirring uniformly, cooling to 35 ℃, adding a foaming agent, rapidly stirring uniformly, pouring into a mold, and freezing in a refrigerator at-40 ℃ for 1 minute until the foaming agent is solidified to form a foam electrolyte layer;
(3) preparation of foam top electrode
Mixing water, bacterial cellulose and a high polymer material, adding an ionophore into the mixture, heating the mixture for 1 to 2 hours at the temperature of between 80 and 100 ℃, cooling the mixture to 75 ℃ after the high polymer material is completely dissolved, adding an emulsifier and esters into the mixture, stirring the mixture for reaction for 2.5 hours, adding a conductive material into the mixture, stirring the mixture to be in a uniform state, cooling the mixture to 35 ℃, adding a foaming agent into the mixture, quickly stirring the mixture uniformly, pouring the mixture onto a foam electrolyte layer in a mold, integrally putting the mixture into a refrigerator, freezing the mixture for 7 hours, melting the mixture for 3 hours, and repeatedly performing three cycles to obtain the porous integrated flexible stretchable touch sensor;
(4) wiring of sensor
The conductive metal wires are pasted at the two ends of the foam electrode by using silver adhesive, so that the sensor is electrically connected with the outside;
(5) Packaging of sensors
And covering a polymer film on the upper surface of the foam upper electrode layer and the lower surface of the foam lower electrode layer to serve as packaging layers, and coating an adhesive on the packaging layers to be adhered to the upper and lower foam electrodes.
The basic working principle of the sensor of the invention is as follows:
when pressure is applied to the sensor, the meshed foam upper electrode layer, the foam lower electrode layer and the foam electrolyte layer of the sensor deform under the action of the pressure, so that the contact area between the electrolyte layer and the electrodes is enlarged, the distance is reduced, and the capacitance is increased; when the pressure disappears, the electrolyte layers of the upper and lower electrodes of the mesh-shaped foam can restore to the original state, and the capacitance can also restore 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.
The foam upper electrode layer, the foam lower electrode layer and the foam electrolyte layer form an electrode or electrolyte interface, when the electrode layer is in contact with the electrolyte layer on two sides, under the action of an external power supply, internal surface charges of the electrode can adsorb ions from the electrolyte, the ions form an interface layer with the same charge quantity as the charge quantity of the internal surface of the electrode on the electrolyte side of the electrode or electrolyte interface and the opposite sign, and because of the potential difference existing on the electrode or electrolyte interface, the charges of the two layers cannot cross the boundary and are neutralized with each other, so that the super capacitor with a stable structure is formed.
Foaming and freezing a mixture consisting of a high polymer material, bacterial cellulose and a conductive material (such as graphene, MXene, CNT and the like) to form a foamed electrode layer, mixing an electrolyte (such as phosphoric acid, sodium hydroxide and sodium carbonate solution) and the bacterial cellulose with the high polymer material, then foaming, preparing a mesh-shaped electrolyte layer after freezing, and then freezing the electrode layer and the electrolyte layer together to integrate the electrode layer and the electrolyte layer. And connecting the prepared sensor to a capacitance measuring circuit to realize pressure mapping. The three parts of the process are all obtained after freezing, and the manufacturing process is simple and quick.
Compared with the prior art, the integrated flexible stretchable touch sensor based on the super-capacitor sensing principle has the following advantages:
(1) the sensor provided by the invention has high tensile rate. The foam electrodes and the foam electrolyte layers of the interdigital electrode type flexible touch sensor based on the super capacitor have the stretching rates of more than 300 percent, and the movement of larger deformation can be monitored, so that the application range of the sensor is widened.
(2) The sensor has good associativity and no gap. The interdigital electrode type flexible touch sensor based on the super capacitor has the advantages that the upper and lower foam electrodes and the foam electrolyte layer are of foam structures, the foam electrodes are formed in one step in the manufacturing process, gaps do not exist among the layers, and the electrodes do not need to be combined through external force.
(3) The sensor provided by the invention is simple in manufacturing process and flexible in size adjustment. The interdigital electrode type flexible touch sensor based on the super capacitor is manufactured after freezing and thawing, other special production requirements are not needed, the area of the sensor can be adjusted according to the using environment, and the sensor can be directly cut.
(4) The sensor provided by the invention has high sensitivity and a large measurement range. This interdigital electrode formula flexible touch sensor based on super capacitor's electrolyte layer contains a large amount of homogeneous network structures, provides a large amount of passageways for the ion, has improved sensitivity, and electrode layer, the electrolyte layer of this sensor contain a large amount of homogeneous network structures, and elasticity is good, has increaseed the test range.
Drawings
FIG. 1 is a schematic view of the overall structure of the sensor of the present invention;
FIG. 2 is a schematic diagram of the sensor of the present invention;
FIG. 3 is a schematic diagram of the working principle of the sensor of the present invention;
fig. 4a-4b are pressure-volume relationship diagrams of the sensor of the present invention.
In the figure: 1. an electrode layer on the foam; 2. a foamed electrolyte layer; 3. a foam lower electrode layer.
Detailed Description
Unless defined otherwise, technical terms used in the following examples have the same meanings as commonly understood by one of ordinary skill in the art to which the present invention belongs. The test reagents used in the following examples, unless otherwise specified, were all conventional biochemical reagents; the experimental methods are all conventional methods unless otherwise specified.
The present invention will be described in detail below with reference to the following examples and the accompanying drawings.
The bacterial cellulose used in the embodiment of the invention is purchased from Beijing Youlan science and technology Limited, and the particle size is 70-150 microns and 100 meshes.
Example 1
The embodiment provides a flexible touch sensor of stretching of integral type based on super capacitor sensing principle for the size of the great position pressure of motion range such as monitoring human body or robot joint, this sensor includes foam top electrode layer 1, foam electrolyte layer 2, foam bottom electrode layer 3 from top to bottom in proper order, and foam electrolyte layer and foam top and bottom electrode layer constitute the sensor.
The sensor manufactured in the embodiment is of a foam-shaped, integrated and three-layer structure, is frozen and then is formed in one step, and is 15mm long, 15mm wide and 2mm thick; the electrode layer is of a mesh foam structure, conductive materials of graphene and PVA are mixed according to a certain proportion, then the mixture is foamed and frozen to obtain the graphene/PVA composite material, the thickness is 0.5mm, the area size can be adjusted according to needs, and the electrode layer in the attached drawings 1 and 2 is 15mm long and 15mm wide; the electrolyte layer is of a mesh foam structure, is prepared by mixing calcium carbonate and PVA, foaming and freezing, and has the thickness of 1 mm; the area can be adjusted as required, and the electrolyte layer in the figure is 15mm long and 15mm wide.
The manufacturing process of the integrated flexible stretchable touch sensor based on the super-capacitor sensing principle is as follows:
1. preparation of foamed lower electrode layer
According to H2And O, weighing PVA and bacterial cellulose in a ratio of 5:1:0.3, mixing the two, adding the mixture into a beaker, adding a magnetic stirrer, covering the mouth of the beaker with tinfoil, putting the beaker into a magnetic water bath kettle, heating the beaker at 80-100 ℃ for 1-2 hours until the PVA is completely dissolved, cooling the water bath kettle to 66 ℃, adding calcium carbonate accounting for 2.27% of the total mass of the solution, adding graphene accounting for 11.33% of the total mass of the solution, cooling the water bath kettle to 60 ℃ after uniformly stirring, adding OP-10 accounting for 5.66% of the total mass of the solution, stirring the dimethyl carbonate accounting for 6.80% of the total mass of the solution for 2 minutes, cooling the water bath to 35 ℃, adding n-pentane accounting for 5.66% of the total mass of the solution, vigorously stirring the mixture, pouring the mixture into a mold, and putting the mold into a refrigerator at-40 ℃ for freezing for 1 minute until the mixture is solidified to serve as a lower electrode layer.
2. Preparation of foamed electrolyte layer
According to H2Weighing PVA and bacterial cellulose in a ratio of 5:1:0.3, mixing the two, adding the mixture into a beaker, adding a magnetic stirrer, covering the opening of the beaker with tinfoil, putting the beaker into a magnetic water bath kettle, heating the beaker at 80-100 ℃ for 1-2 hours until the PVA is completely dissolved, cooling the water bath kettle to 66 ℃, adding calcium carbonate accounting for 2.55 percent of the total mass of the solution, cooling the water bath kettle to 60 ℃ after uniformly stirring, adding OP-10 accounting for 6.39 percent of the total mass of the solution, stirring dimethyl carbonate accounting for 7.66 percent of the total mass of the solution for 2 minutes, and stirring the mixture Cooling to 35 deg.C in water bath, adding n-pentane 6.39% of the total solution, stirring, pouring onto the lower electrode layer of foam in a mold, and freezing in a-40 deg.C freezer for 1 min until it solidifies to obtain the electrolyte layer.
3. Preparation of foam top electrode
According to H2O: PVA: weighing bacterial cellulose at a ratio of 5:1:0.3, mixing the bacterial cellulose and the bacterial cellulose, adding the mixture into a beaker, putting a magnetic stirrer, covering the opening of the beaker with tinfoil, putting the beaker into a magnetic water bath, heating for 1-2 hours at the temperature of 80-100 ℃ until PVA is completely dissolved, then cooling the water bath to 66 ℃, adding calcium carbonate accounting for 2.27 percent of the total mass of the solution, adding graphene accounting for 11.33 percent of the total mass of the solution, stirring uniformly, cooling the water bath to 60 ℃, adding OP-10 accounting for 5.66 percent of the total mass of the solution and dimethyl carbonate accounting for 6.80 percent of the total mass of the solution, stirring for 2 minutes, cooling the water bath to 35 ℃, adding n-pentane accounting for 5.66 percent of the total mass of the solution, stirring vigorously, pouring onto a foam electrolyte layer in a mould, freezing for 7 hours in a freezer at the temperature of-40 ℃ as a whole, melting for 3 hours, and repeating three cycles to obtain the integrated flexible stretchable touch sensor with the hole shape.
4. Wiring of sensor
And silver adhesive is used for adhering conductive metal wires at two ends of the foam electrode, so that the sensor is electrically connected with the outside.
5. Packaging of sensors
The upper and lower foam electrode foam layers can be covered with polymer films as packaging layers, and PVA solution is coated on the packaging layers and then is bonded with the upper and lower foam electrodes.
Example 2
The embodiment provides a flexible touch sensor of stretching of integral type based on super capacitor sensing principle for the size of the great position pressure of motion range such as monitoring human body or robot joint, this sensor includes foam top electrode layer 1, foam electrolyte layer 2, foam bottom electrode layer 3 from top to bottom in proper order, and foam electrolyte layer constitutes the sensor with upper and lower foam electrode layer.
The sensor manufactured in the embodiment is of a foam-shaped, integrated and three-layer structure, is frozen and then is formed in one step, and is 15mm long, 15mm wide and 2mm thick; the electrode layer is of a mesh foam structure, conductive materials of polypyrrole and PVA are mixed according to a certain proportion, then foaming and freezing are carried out, the thickness is 0.5mm, the area size can be adjusted according to needs, and the electrode layer in the attached drawing is 15mm in length and 15mm in width; the electrolyte layer is of a mesh foam structure, is prepared by mixing calcium carbonate and PVA, foaming and freezing, and has the thickness of 1 mm; the area can be adjusted as required, and the electrolyte layer in the figure is 15mm long and 15mm wide.
The manufacturing process of the integrated flexible stretchable touch sensor based on the super-capacitor sensing principle is as follows:
1. preparation of foamed lower electrode layer
According to H2And O, weighing PVA and bacterial cellulose in a ratio of 5:1:0.3, mixing the two, adding the mixture into a beaker, adding a magnetic stirrer, covering the mouth of the beaker with tinfoil, putting the beaker into a magnetic water bath kettle, heating the beaker at 80-100 ℃ for 1-2 hours until the PVA is completely dissolved, cooling the water bath kettle to 66 ℃, adding calcium carbonate accounting for 2.27% of the total mass of the solution, adding polypyrrole accounting for 11.33% of the total mass of the solution, cooling the water bath kettle to 60 ℃ after uniformly stirring, adding OP-10 accounting for 5.66% of the total mass of the solution, stirring the dimethyl carbonate accounting for 6.80% of the total mass of the solution for 2 minutes, cooling the water bath to 35 ℃, adding n-pentane accounting for 5.66% of the total mass of the solution, vigorously stirring the mixture, pouring the mixture into a mold, and putting the mold into a refrigerator at-40 ℃ for freezing for 1 minute until the mixture is solidified to serve as a lower electrode layer.
2. Preparation of foamed electrolyte layer
According to H2Weighing PVA and bacterial cellulose in a ratio of 5:1:0.3, mixing the two, adding the mixture into a beaker, adding a magnetic stirrer, covering the opening of the beaker with tinfoil, putting the beaker into a magnetic water bath kettle, heating the beaker at 80-100 ℃ for 1-2 hours until the PVA is completely dissolved, cooling the water bath kettle to 66 ℃, adding calcium carbonate accounting for 2.55 percent of the total mass of the solution, cooling the water bath kettle to 60 ℃ after uniformly stirring, adding OP-10 accounting for 6.39 percent of the total mass of the solution and 7.66 percent of carbonic acid di (carbonic acid) accounting for 7.66 percent of the total mass of the solution Stirring the methyl ester for 2 minutes, cooling the methyl ester to 35 ℃ in a water bath, adding n-pentane accounting for 6.39% of the total mass of the solution, stirring vigorously, pouring the mixture onto a lower electrode layer in a mold, and putting the mixture into a freezer at the temperature of minus 40 ℃ for freezing for 1 minute until the mixture is solidified to be used as an electrolyte layer.
3. Preparation of foam top electrode
According to H2O: PVA: weighing bacterial cellulose at a ratio of 5:1:0.3, mixing the bacterial cellulose and the bacterial cellulose, adding the mixture into a beaker, putting a magnetic stirrer, covering the opening of the beaker with tinfoil, putting the beaker into a magnetic water bath, heating for 1-2 hours at the temperature of 80-100 ℃ until PVA is completely dissolved, then cooling the water bath to 66 ℃, adding calcium carbonate accounting for 2.27 percent of the total mass of the solution, adding polypyrrole accounting for 11.33 percent of the total mass of the solution, stirring uniformly, cooling the water bath to 60 ℃, adding OP-10 accounting for 5.66 percent of the total mass of the solution and dimethyl carbonate accounting for 6.80 percent of the total mass of the solution, stirring for 2 minutes, cooling the water bath to 35 ℃, adding n-pentane accounting for 5.66 percent of the total mass of the solution, stirring vigorously, pouring onto an electrolyte layer in a mould, putting the whole into a freezer at the temperature of minus 40 ℃ for freezing for 7 hours, melting for 3 hours, and repeating three cycles to obtain the integrated flexible stretchable touch sensor with the hole shape.
4. Wiring of sensor
And silver adhesive is used for adhering conductive metal wires at two ends of the foam electrode, so that the sensor is electrically connected with the outside.
5. Packaging of sensors
The upper and lower foam electrode foam layers can be covered with polymer films as packaging layers, and PVA solution is smeared on the packaging layers and then is bonded with the upper and lower foam electrodes.
Example 3
The embodiment provides a flexible touch sensor of stretching of integral type based on super capacitor sensing principle for the size of the great position pressure of motion range such as monitoring human body or robot joint, this sensor includes foam top electrode layer 1, foam electrolyte layer 2, foam bottom electrode layer 3 from top to bottom in proper order, and foam electrolyte layer constitutes the sensor with upper and lower foam electrode layer.
The sensor manufactured in the embodiment is of a foam-shaped, integrated and three-layer structure, is frozen and then is formed in one step, and is 15mm long, 15mm wide and 2mm thick; the electrode layer is of a mesh foam structure, conductive materials of graphene and ethylene carbonate are mixed according to a certain proportion, then the mixture is foamed and frozen to obtain the graphene/ethylene carbonate composite material, the thickness of the graphene/ethylene carbonate composite material is 0.5mm, the area size of the graphene/ethylene carbonate composite material can be adjusted according to needs, and the electrode layer in the drawing is 15mm in length and 15mm in width; the electrolyte layer is of a mesh foam structure, is prepared by mixing calcium carbonate and PVA, foaming and freezing, and has the thickness of 1 mm; the area can be adjusted as required, and the electrolyte layer in the figure is 15mm long and 15mm wide.
The manufacturing process of the integrated flexible stretchable touch sensor based on the super-capacitor sensing principle is as follows:
1. preparation of foamed lower electrode layer
According to H2Weighing PVA and bacterial cellulose in a ratio of 5:1:0.3, mixing the two, adding the mixture into a beaker, adding a magnetic stirrer, covering the mouth of the beaker with tinfoil, putting the beaker into a magnetic water bath kettle, heating the beaker at 80-100 ℃ for 1-2 hours until the PVA is completely dissolved, cooling the water bath kettle to 66 ℃, adding calcium carbonate accounting for 2.27% of the total mass of the solution, adding graphene accounting for 11.33% of the total mass of the solution, cooling the water bath kettle to 60 ℃ after stirring uniformly, adding OP-10 accounting for 5.66% of the total mass of the solution, stirring the ethylene carbonate accounting for 6.80% of the total mass of the solution for 2 minutes, cooling the water bath to 35 ℃, adding n-pentane accounting for 5.66% of the total mass of the solution, stirring vigorously, pouring the mixture into a mold, and putting the mold into a refrigerator at-40 ℃ for freezing for 1 minute until the mixture is solidified to serve as a lower electrode layer.
2. Preparation of foamed electrolyte layer
According to H2Weighing PVA and bacterial cellulose in a ratio of 5:1:0.3, mixing the two, adding the mixture into a beaker, adding a magnetic stirrer, covering the opening of the beaker with tinfoil, putting the beaker into a magnetic water bath kettle, heating the beaker at 80-100 ℃ for 1-2 hours until the PVA is completely dissolved, cooling the water bath kettle to 66 ℃, adding calcium carbonate accounting for 2.55 percent of the total mass of the solution, cooling the water bath kettle to 60 ℃ after stirring the mixture evenly, adding OP-10 accounting for 6.39 percent of the total mass of the solution, and adding the PVA and the bacterial cellulose into the beaker Stirring 7.66% ethylene carbonate for 2 min, cooling to 35 deg.C, adding n-pentane (6.39% of total solution mass), stirring, pouring onto the lower electrode layer of the mold, and freezing at-40 deg.C for 1 min to solidify to obtain the electrolyte layer.
3. Preparation of foam top electrode
According to H2O: PVA: weighing bacterial cellulose at a ratio of 5:1:0.3, mixing the bacterial cellulose and the bacterial cellulose, adding the mixture into a beaker, putting a magnetic stirrer, covering the opening of the beaker with tinfoil, putting the beaker into a magnetic water bath, heating for 1-2 hours at the temperature of 80-100 ℃ until PVA is completely dissolved, then cooling the water bath to 66 ℃, adding calcium carbonate accounting for 2.27 percent of the total mass of the solution, adding graphene accounting for 11.33 percent of the total mass of the solution, stirring uniformly, cooling the water bath to 60 ℃, adding OP-10 accounting for 5.66 percent of the total mass of the solution and ethylene carbonate accounting for 6.80 percent of the total mass of the solution, stirring for 2 minutes, cooling the water bath to 35 ℃, adding n-pentane accounting for 5.66 percent of the total mass of the solution, stirring vigorously, pouring onto an electrolyte layer in a mould, freezing for 7 hours in a freezer at the temperature of-40 ℃ as a whole, melting for 3 hours, and repeating three cycles to obtain the integrated flexible stretchable touch sensor with the hole shape.
4. Wiring of sensor
And silver adhesive is used for adhering conductive metal wires at two ends of the foam electrode, so that the sensor is electrically connected with the outside.
5. Packaging of sensors
The upper and lower foam electrode foam layers can be covered with polymer films as packaging layers, and PVA solution is smeared on the packaging layers and then is bonded with the upper and lower foam electrodes.
As shown in fig. 3, under the action of pressure, physical contact is generated between the mesh-shaped electrolyte layer and the mesh-shaped electrode, the contact area increases with the increase of the load, and when the load disappears, the sensor returns to the original state and the capacitance value returns to the initial value; under the action of tensile force, physical contact is generated between the mesh-shaped electrolyte layer and the mesh-shaped electrode, the contact area is increased along with the increase of the load, when the load disappears, the sensor returns to the original state, and the capacitance value returns to the initial value.
In order to verify the static characteristics of the tactile sensor, the wire of the sensor is first connected to an LCR meter, and then the relationship between the sensor capacitance and pressure is measured using a weight and the LCR meter, resulting in the capacitance curves shown in FIGS. 4a and 4 b. As can be seen from the graph, the capacitance values of the sensors obtained under different formulations and different pressures can stably and accurately reflect the external pressure. In embodiment 2, the polypyrrole is replaced with the graphene which is a conductive material on the basis of embodiment 1, and the capacitance value of embodiment 1 is smaller than that of embodiment 2 under the same pressure, so that the difference in device performance caused by the difference in conductivity between the conductive materials can be seen, but the experimental purpose can be achieved. In example 3, in addition to example 1, the sensor may be made porous by replacing dimethyl carbonate with ethylene carbonate, and has a high elongation and a high sensitivity. .
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents, improvements and the like that fall within the spirit and principle of the present invention are intended to be included therein.
Claims (10)
1. The utility model provides a flexible tactile sensor that stretches of integral type which is based on super capacitor sensing principle which characterized in that: the foam electrolyte layer is prepared by foaming a mixture comprising a solvent, a high polymer material, esters, an ionophore and bacterial cellulose, wherein the mass ratio of the five is (25-30) to (3-4): (4-6) (1-2) (0.4-0.6), wherein the foam upper electrode layer and the foam lower electrode layer are made of the same material and are prepared by foaming a mixture comprising a solvent, a high polymer material, esters, a conductive material and bacterial cellulose, and the mass ratio of the five materials is (25-30): (3-4): (4-6): (3-4): 0.4-0.6);
the sensor is characterized in that a mixture consisting of a high polymer material, bacterial cellulose and a conductive material is foamed and frozen to form a foamed electrode layer, an electrolyte, the bacterial cellulose and the high polymer material are mixed and then foamed, a mesh-shaped electrolyte layer is prepared after freezing, and then the electrode layer and the electrolyte layer are frozen together and combined into a whole.
2. The integrated flexible stretchable touch sensor based on the super capacitor sensing principle according to claim 1, characterized in that: the solvent is water or ionic liquid, wherein the ionic liquid is liquid at room temperature or near room temperature and is completely formed by organic cations and inorganic or organic anions, the cations comprise quaternary ammonium salt ions, quaternary phosphonium salt ions, imidazolium salt ions and pyrrole salt ions, and the anions comprise halogen ions, tetrafluoroborate ions and hexafluorophosphate ions.
3. The integrated flexible stretchable touch sensor based on the super capacitor sensing principle according to claim 1, characterized in that: the high polymer material comprises polyvinyl alcohol, thermoplastic polyurethane elastomer or polystyrene.
4. The integrated flexible stretchable touch sensor based on the super capacitor sensing principle as claimed in claim 1, wherein: the esters comprise one or a mixture of more than two of propylene carbonate, ethylene carbonate, ethyl methyl carbonate, dimethyl carbonate and ethylene carbonate.
5. The integrated flexible stretchable touch sensor based on the super capacitor sensing principle as claimed in claim 1, wherein: the ionic carrier is one or a mixture of more than two of acid, alkali and salt.
6. The integrated flexible stretchable touch sensor based on the super capacitor sensing principle according to claim 1, characterized in that: the conductive material is metal, carbon or conductive polymer, and comprises one or a compound of more than two of copper, aluminum, gold, silver, nickel, graphite, acetylene black, carbon nano tubes, graphene, MXene, polypyrrole and polythiophene.
7. The integrated flexible stretchable touch sensor based on the super capacitor sensing principle according to claim 1, characterized in that: the thickness of the foam upper electrode layer and the thickness of the foam lower electrode layer are both smaller than that of the foam electrolyte layer.
8. The integrated flexible stretchable touch sensor based on the super capacitor sensing principle as claimed in claim 1, wherein: the flexible stretchable touch sensor has a shape including a rectangular parallelepiped, a cylinder, and a triangular pyramid.
9. The integrated flexible stretchable touch sensor based on the super capacitor sensing principle as claimed in claim 1, wherein: the sensor is electrically connected with the outside through pasting conductive metal wires at two ends of the foam upper electrode layer and the foam lower electrode layer by using silver glue, and polymer films are covered on the upper surface of the foam upper electrode layer and the lower surface of the foam lower electrode layer to serve as packaging layers.
10. The method for preparing an integrated flexible stretchable touch sensor based on the super capacitor sensing principle as recited in any one of claims 1 to 9, wherein: the method specifically comprises the following steps:
(1) preparation of foamed lower electrode layer
Mixing water, bacterial cellulose and a high polymer material, adding an ionophore, heating for 1-2 hours at 80-100 ℃, cooling to 75 ℃ after the high polymer material is completely dissolved, adding an emulsifier and esters, stirring for reaction for 2.5 hours, adding a conductive material, stirring to be in a uniform state, cooling to 35 ℃, adding a foaming agent, quickly stirring uniformly, pouring into a mold, and putting into a refrigerator to freeze until the mixture is solidified to be used as a lower electrode layer of foam;
(2) preparation of foamed electrolyte layer
Mixing water, bacterial cellulose and a high polymer material, adding an ionophore, heating for 1-2 hours at 80-100 ℃, cooling to 75 ℃ after the high polymer material is completely dissolved, adding an emulsifier and esters, stirring uniformly, cooling to 35 ℃, adding a foaming agent, rapidly stirring uniformly, pouring onto a prepared foam lower electrode layer in a mold, and putting into a refrigerator for freezing until the mixture is solidified to serve as a foam electrolyte layer;
(3) preparation of foam top electrode
Mixing water, bacterial cellulose and a high polymer material, adding an ionophore into the mixture, heating the mixture for 1 to 2 hours at the temperature of between 80 and 100 ℃, cooling the mixture to 75 ℃ after the high polymer material is completely dissolved, adding an emulsifier and esters into the mixture, stirring the mixture for reaction for 2.5 hours, adding a conductive material into the mixture, stirring the mixture to be in a uniform state, cooling the mixture to 35 ℃, adding a foaming agent into the mixture, quickly stirring the mixture uniformly, pouring the mixture onto a foam electrolyte layer in a mold, integrally putting the mixture into a refrigerator, freezing the mixture for 7 hours, melting the mixture for 3 hours, and repeatedly performing three cycles to obtain the porous integrated flexible stretchable touch sensor;
(4) wiring of sensor
The conductive metal wires are pasted at the two ends of the foam electrode by using silver adhesive, so that the sensor is electrically connected with the outside;
(5) packaging of sensors
And covering a polymer film on the upper surface of the foam upper electrode layer and the lower surface of the foam lower electrode layer to serve as packaging layers, and coating an adhesive on the packaging layers to be adhered to the upper and lower foam electrodes.
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| CN112461414B (en) * | 2020-11-18 | 2022-01-28 | 南京邮电大学 | Sensor with conductive foam electrode combined with flexible strain gauge and preparation method |
| CN113155326A (en) * | 2021-03-09 | 2021-07-23 | 河北工业大学 | Flexible self-supporting fiber woven touch sensor |
| CN113932950A (en) * | 2021-10-13 | 2022-01-14 | 中国科学院苏州纳米技术与纳米仿生研究所 | Flexible pressure sensor and manufacturing method thereof |
| CN114112119A (en) * | 2021-11-19 | 2022-03-01 | 河北工业大学 | Microstructured touch sensor based on pseudo-capacitance principle and preparation method thereof |
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