WO2022204932A1 - Bionic microarray flexible electrode and preparation method therefor, and flexible pressure sensor - Google Patents

Bionic microarray flexible electrode and preparation method therefor, and flexible pressure sensor Download PDF

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Publication number
WO2022204932A1
WO2022204932A1 PCT/CN2021/083921 CN2021083921W WO2022204932A1 WO 2022204932 A1 WO2022204932 A1 WO 2022204932A1 CN 2021083921 W CN2021083921 W CN 2021083921W WO 2022204932 A1 WO2022204932 A1 WO 2022204932A1
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pdms
microarray
mold
flexible
biomimetic
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PCT/CN2021/083921
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French (fr)
Chinese (zh)
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李晖
陈静
李林
王磊
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中国科学院深圳先进技术研究院
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Priority to PCT/CN2021/083921 priority Critical patent/WO2022204932A1/en
Publication of WO2022204932A1 publication Critical patent/WO2022204932A1/en

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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
    • G01L1/14—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
    • 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
    • G01L9/12—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 capacitance, i.e. electric circuits therefor

Definitions

  • the invention relates to the technical field of flexible wearable health electronic devices, in particular to a biomimetic microarray flexible electrode, a preparation method thereof, and a flexible pressure sensor.
  • the flexible pressure sensor plays an increasingly important role in medical health, motion detection and correction, etc. important role.
  • the flexible pressure sensor has the characteristics of good conformability, lightness and portability.
  • Medical wearable devices based on flexible pressure sensors can be integrated into clothing, accessories, or directly attached to the skin surface to dynamically collect human physiological information for feedback and judgment of human health.
  • the flexible pressure sensor can be arbitrarily attached to the surface of an irregular three-dimensional object for signal detection according to the usage scene. For example, it can be attached to the throat to monitor the vibration of the vocal cords. and frequency monitoring, etc.
  • Flexible pressure sensors with excellent electrical properties mainly include high-performance flexible substrate electrodes and sensitive materials, which are realized in combination with special structures.
  • flexible pressure sensors are mostly prepared by methods such as silicon wafer etching, vapor deposition, and high-resolution 3D printing, which are complicated in process, expensive and energy-intensive. The high manufacturing cost limits its development and application in real life.
  • most flexible pressure sensors have low sensitivity, narrow measurement range, and cannot actively identify weak physiological signals.
  • the present invention proposes a bionic microarray flexible electrode, a preparation method thereof, and a flexible pressure sensor to solve or partially solve the technical problems existing in the prior art.
  • the present invention provides a preparation method of a biomimetic microarray flexible electrode, comprising the following steps:
  • the PDMS prepolymer is mixed with the curing agent, the PDMS mixture is obtained, which is for subsequent use;
  • the PDMS mixture is poured on the plant leaves, the PDMS is cured, and the cured PDMS is taken out from the plant leaves to obtain a mold whose surface is opposite to the surface of the plant leaves;
  • the surface of the mold opposite to the surface of the plant leaf is attached to the template provided with a plurality of through holes, the template is placed in a vacuum adsorption device, the vacuum adsorption is turned on, and the mold is separated from the template;
  • AgNWs dispersion liquid is prepared, the AgNWs dispersion liquid is sprayed onto the mold after vacuum adsorption, and annealed to obtain a biomimetic microarray flexible electrode.
  • the preparation method of the biomimetic microarray flexible electrode further comprises, before attaching the surface of the mold opposite to the surface of the plant leaf on the template provided with a plurality of through holes : drop the PDMS mixture into the surface of the mold opposite to the surface of the plant leaf, spin-coat, cure, and remove the cured PDMS from the mold to obtain a PDMS film with a micro-cone surface; The micro-conical surface of the PDMS film is attached to the template with a plurality of through holes, and then vacuum adsorption is performed to separate the PDMS film and the template; and then the AgNWs dispersion is sprayed onto the PDMS film after vacuum adsorption. , after annealing treatment, the biomimetic microarray flexible electrode is obtained.
  • the preparation method of the biomimetic microarray flexible electrode, before spraying the AgNWs dispersion on the PDMS film after vacuum adsorption further comprises: dropping the PDMS mixture into the PDMS film far away from the PDMS film.
  • the surface of the cone is spin-coated, and the PDMS is cured, and then the cured PDMS film is separated from the template; the AgNWs dispersion is then sprayed onto the cured PDMS film, and annealed to obtain a biomimetic microarray.
  • Array of flexible electrodes Array of flexible electrodes.
  • the preparation method of the biomimetic microarray flexible electrode, before dropping the PDMS mixture into the surface of the mold opposite to the surface of the plant leaf further comprises: placing the mold in an alcohol solution for passivation.
  • the PDMS mixture is dropped into the surface of the mold opposite to the surface of the plant leaf, and then spin-coated and cured.
  • Spin coating at 500r/min for 10-20s; curing is as follows: curing at 80-100°C for 20-40min.
  • the PDMS mixture is dropped into the surface of the PDMS film away from the side of the microcone, and then spin-coated, and the PDMS is cured, wherein the spin-coating is performed.
  • spin coating at a speed of 300-500r/min for 8-12s; curing is as follows: first heating and curing under an infrared lamp for 10-20min, and then heating in an oven at 80-100°C for 40-60min.
  • the preparation method of the AgNWs dispersion is as follows: adding the AgNWs into anhydrous ethanol and ultrasonically dispersing to obtain the AgNWs dispersion ;
  • the annealing treatment is specifically: annealing treatment in an oven at 80-100° C. for 40-60 minutes.
  • the present invention also provides a biomimetic microarray flexible electrode, which is prepared by the preparation method.
  • the present invention also provides a flexible pressure sensor, comprising:
  • the ion gel dielectric layer is located between a pair of the flexible electrodes of the biomimetic microarray.
  • the preparation method of the ion gel dielectric layer comprises the following steps:
  • the mixed solution is coated on the substrate, then annealed, and the ion gel dielectric layer is obtained by peeling off.
  • a plant leaf with a unique micron-scale conical array structure on the surface is used as a template to prepare a mold, and a millimeter-scale semicircular convex array formed by vacuum adsorption is combined to form It has a three-dimensional array structure with different sizes such as micrometers to millimeters.
  • the microarray flexible electrodes with this structure make the sensor have good response characteristics to pressures of different magnitudes, and the measurement range is greatly expanded;
  • the response of the flexible pressure sensor of the present invention to the pressure is completed by the changes of the flexible electrodes of the microarray structures of different sizes and the change of the interfacial capacitance of the ion gel layer.
  • the specific capacitance makes the pressure sensor have a more significant capacitance change than ordinary capacitive flexible sensors in the face of external pressure, so that the sensor has extremely high sensitivity and responsiveness; at the same time, the pressure sensor of the present application has a simple structure and manufacturing steps. It is easy, which greatly reduces the production cost and processing difficulty.
  • Fig. 1 is the preparation method of a kind of biomimetic microarray flexible electrode of the present invention, wherein in one embodiment, the schematic diagram of pouring PDMS mixture on the surface of velvet arrowroot leaves;
  • FIG. 2 is a schematic diagram of a preparation method of a biomimetic microarray flexible electrode of the present invention, wherein in one embodiment, the PDMS mixture is continuously spin-coated on the surface of the formed mold;
  • FIG. 3 is a schematic diagram of a method for preparing a bionic microarray flexible electrode of the present invention, wherein in one embodiment, a PDMS film is adhered to a template provided with a plurality of through holes;
  • FIG. 4 is a method for preparing a biomimetic microarray flexible electrode according to the present invention, and a schematic structural diagram of a biomimetic microarray flexible electrode in one embodiment
  • FIG. 5 is a schematic structural diagram of the flexible pressure sensor of the present invention.
  • FIG. 6 is a schematic diagram of the flexible pressure sensor of the present invention, wherein an ionogel dielectric layer is prepared on a substrate in one embodiment
  • FIG. 7 is a surface topography diagram of the biomimetic microarray flexible electrode prepared in Example 1 of the present invention.
  • Fig. 8 is the sensitivity and response curve diagram of the flexible pressure sensor assembled in embodiment 1 of the present invention.
  • FIG. 9 is a graph showing the detection of human pulse of the flexible pressure sensor assembled in Embodiment 1 of the present invention.
  • FIG. 10 is a graph showing the detection of the pressure on the sole of the human body by the flexible pressure sensor assembled in Embodiment 1 of the present invention.
  • the invention provides a preparation method of a bionic microarray flexible electrode, comprising the following steps:
  • S1 provide a plant leaf with foliar texture
  • the PDMS mixture is obtained after mixing the PDMS prepolymer and the curing agent, and is for subsequent use;
  • the plant leaf with leaf surface texture refers to the clear texture on the surface of the plant leaf, and the surface forms a similar micron-scale micro-convex cone array structure, such as this one.
  • Plant leaves include velvet arrowroot leaves, watermelon rinds, pepper grass leaves, narrow-leaf tamarisk leaves, Xiao arrowroot leaves, etc.
  • the plant leaves can be fixed on the substrate, and then the PDMS mixture is poured.
  • the substrate can be acrylic plate, obviously using Other plates that can play the role of a carrier can be used; the plant leaves can be fixed on the substrate by double-sided tape, and for the velvet arrowroot leaves, the front of the leaf can be fixed on the substrate; the PDMS mixture is poured on the substrate.
  • the PDMS is cured to obtain a mold, one surface of the mold has an array structure opposite to the micro-convex pyramid array structure on the surface of the plant leaf, that is, a micro-concave pyramid structure is formed; the surface of the mold opposite to the surface of the plant leaf is attached On a template with a plurality of through holes, the surface of the mold with the micro-concave pyramid structure is attached to the template, the through holes on the template are arranged in an array, and the diameters of the through holes can be the same or different, and the diameter of the through holes can be the same or different.
  • the mold is adhered to the template with PET substrate double-sided tape.
  • the mold After vacuum adsorption, the mold will form a millimeter-scale shape on the template with the opposite surface to the surface of the plant leaf and the corresponding through-hole area due to the pressure difference between the upper and lower surfaces of the mold.
  • a semicircular concave structure and then spraying the AgNWs (silver nanowire) dispersion to the surface of the mold after vacuum adsorption, which is opposite to the surface of the plant leaf, to obtain a biomimetic microarray flexible electrode.
  • the method before pouring the PDMS mixture on the plant leaves, the method further includes: washing the plant leaves in deionized water for 2-4 minutes, and then blowing dry with nitrogen gas.
  • the PDMS mixture is obtained after mixing the PDMS prepolymer and the curing agent, wherein the mass ratio of the PDMS (polydimethylsiloxane) prepolymer to the curing agent is 10:(1-3),
  • the PDMS prepolymer model is Dow Corning 184, and the curing agent is Dow Corning 184.
  • the method before pouring the PDMS mixture on the plant leaves, the method further comprises: putting the PDMS mixture into a blender and stirring and degassing for 3-5 minutes.
  • the method before attaching the surface of the mold opposite to the surface of the plant leaves on the template provided with the plurality of through holes, the method further includes: dropping the PDMS mixture into the surface of the mold opposite to the surface of the plant leaves, and then rotating the mold. Coating, curing, and then removing the cured PDMS from the mold to obtain a PDMS film with a micro-cone surface; then attaching the micro-cone surface of the PDMS film to a template with multiple through holes, and then After vacuum adsorption, the PDMS film and the template were separated; then, the AgNWs dispersion was sprayed onto the PDMS film after vacuum adsorption, and annealed to obtain a biomimetic microarray flexible electrode.
  • the PDMS mixture was dropped onto the surface of the mold, and after curing, a PDMS film was obtained.
  • the surface of the PDMS film was in the shape of a microcone. Specifically, the surface of the PDMS film had the same surface microconvex cone as the plant leaf. Array structure; when spraying, the AgNWs dispersion was sprayed onto the surface of the PDMS film in the form of microcones.
  • the method before spraying the AgNWs dispersion on the PDMS film after vacuum adsorption, the method further includes: dropping the PDMS mixture onto the surface of the PDMS film away from the side of the microcone, spin coating, and making The PDMS is cured, and then the cured PDMS film is separated from the template; the AgNWs dispersion is sprayed onto the cured PDMS film, and annealed to obtain a biomimetic microarray flexible electrode.
  • the PDMS mixture was dropped again on the surface of the PDMS film, and the AgNWs dispersion was sprayed.
  • the biomimetic microarray flexible electrodes prepared in this way formed a multi-level upper and lower plate structure, which has good resistance to pressures of different magnitudes. response characteristics.
  • prior to dropping the PDMS mixture onto the surface of the mold opposite to the surface of the plant leaves further comprises: placing the mold in an alcohol solution for passivation.
  • the alcohol solution is an anhydrous ethanol solution; specifically, in practice, the mold is first placed in a plasma cleaning machine and treated with oxygen plasma for 2 to 4 minutes, then the mold is immersed in an anhydrous ethanol solution, and then placed in a vacuum drying box at Dry at 70-80°C for 1-3 hours, and blow dry the mold with nitrogen after taking it out; the surface of the mold is made hydrophobic by passivation, which facilitates the removal of the PDMS film from the mold.
  • the PDMS mixture is dropped into the surface of the mold opposite to the surface of the plant leaf, and then spin-coated and cured, wherein the spin-coating is specifically: spin-coating at a rotational speed of 300-500 r/min for 10-20 s; curing; Specifically: curing at 80 to 100 ° C for 20 to 40 minutes.
  • the PDMS mixture is dropped onto the surface of the PDMS film away from the micro-cone, and then spin-coated, and the PDMS is cured.
  • curing is as follows: firstly heating and curing under infrared lamp for 10 ⁇ 20min, and then heating in an oven at 80 ⁇ 100°C for 40 ⁇ 60min.
  • the preparation method of the AgNWs dispersion is as follows: adding the AgNWs into anhydrous ethanol, and ultrasonically dispersing to obtain the AgNWs dispersion;
  • the annealing treatment is specifically: annealing treatment in an oven at 80-100° C. for 40-60 minutes.
  • the mass ratio of AgNWs (silver nanowires) to absolute ethanol is 1:(5-10).
  • the AgNWs dispersion is sprayed onto the surface of the cured PDMS film until the surface resistance value of the PDMS film is 10-30 ⁇ , and annealed in an oven at 80-100°C for 40-60min to make the AgNWs dispersion in the solvent complete evaporation, thereby forming AgNWs on the surface of PDMS films and increasing the adhesion between AgNWs and PDMS films.
  • the method before spraying the AgNWs dispersion onto the PDMS thin film, the method further includes: placing the PDMS thin film in a plasma cleaning machine and treating it with oxygen plasma for 3-5 minutes to improve the adhesion ability on the surface of the PDMS thin film.
  • Figures 1-4 show schematic diagrams of biomimetic microarray flexible electrodes prepared from velvet arrowroot leaves in one of the embodiments.
  • Fig. 1 is the schematic diagram of pouring PDMS mixture 2 on the surface of velvet arrowroot blade 1, after curing, a mold is formed, and the surface of velvet arrowroot blade 1 has a slightly convex cone array structure;
  • Fig. 2 is a continuous spin coating on the surface of the formed mold 3 PDMS mixture 2, after curing, take out PDMS from mold 3 to obtain a PDMS film.
  • the surface of the PDMS film has an opposite structure to that of mold 3, and has the same microstructure as the surface of velvet arrowroot blade 1, which is mentioned above.
  • Figure 3 shows that the PDMS film 4 is adhered to the template 5 with a plurality of through holes 51, and after vacuum adsorption, a concave shape 41 is formed on the PDMS film 4 corresponding to the through holes 51, and then continues on The surface of the PDMS film 4 away from the micro-cone side continues to spin-coat the PDMS mixture 2.
  • the AgNWs dispersion is sprayed onto the surface of the PDMS film 4 with the micro-cone structure, and AgNWs61 are formed on the surface, and finally the obtained
  • the structure of the biomimetic microarray flexible electrode 6 is shown in Figure 4.
  • the present invention also provides a flexible pressure sensor, as shown in FIG. 5 , including:
  • a pair of biomimetic microarray flexible electrodes 6 prepared by the above method
  • the ion gel dielectric layer 7 is located between a pair of flexible electrodes 6 of a bionic microarray.
  • the assembling method of the above-mentioned flexible pressure sensor includes the following steps:
  • Lead wires are drawn from the edges of the above two bionic microarray flexible electrodes 6 respectively, and the wires and electrodes are bonded with conductive silver paste, and then placed in an oven at 80-100°C for curing for 40-60min; then the ion gel dielectric layer 7 is placed on the Between the two biomimetic microarray flexible electrodes 6, the periphery of the biomimetic microarray flexible electrodes 6 is sealed with polyimide tape, and the flexible pressure sensor is assembled.
  • the preparation method of the ion gel dielectric layer 7 includes the following steps:
  • PVDF-HFP polyvinylidene fluoride-hexafluoropropylene copolymer
  • the mixed solution is coated on the substrate, then annealed, and the ion gel dielectric layer is obtained by peeling off.
  • the ionic liquid in this application is EMIM TFSI (1-ethyl-3-methylimidazole bis-trifluoromethanesulfonimide salt), and PVDF-HFP (polyvinylidene fluoride-hexafluoropropylene copolymer) ) was added to acetone, and stirred at 50 to 70 ° C for 2 to 4 hours, so that PVDF-HFP was melted and uniformly dispersed in the acetone solvent; then the ionic liquid EMIM TFSI was added and stirred at room temperature for 1 to 2 hours to obtain a mixed solution.
  • EMIM TFSI 1-ethyl-3-methylimidazole bis-trifluoromethanesulfonimide salt
  • PVDF-HFP polyvinylidene fluoride-hexafluoropropylene copolymer
  • the substrate is a glass substrate
  • the above mixed solution is spin-coated on the glass substrate at a speed of 300-500 r/min for 40-60 seconds, and then placed in a vacuum drying oven at a temperature of 40-60° C. for annealing For 1 to 3 hours, the solvent in the mixed solution is completely removed, and the ion gel dielectric layer is obtained after peeling off.
  • FIG. 6 shows a schematic diagram of preparing the ion gel dielectric layer 7 on the substrate 8 .
  • a plant leaf with a unique micron-level cone array structure on the surface is used as a template to prepare a mold, and then the mold is further used to form a PDMS film with the same microstructure array as the surface of the plant leaf
  • a three-dimensional array structure with different sizes from micrometers to millimeters is formed.
  • the microarray flexible electrodes with this structure make the sensor have good response characteristics to pressures of different magnitudes. , the measurement range is greatly expanded.
  • the response to pressure is completed by the changes of the flexible electrodes of the microarray structures of different sizes and the change of the interfacial capacitance of the ion gel layer.
  • the embodiment of the present application provides a preparation method of a biomimetic microarray flexible electrode, comprising the following steps:
  • A2 Mix the PDMS prepolymer poly(dimethyl-methylvinylsiloxane) and the curing agent poly(dimethyl-methylhydrogenosiloxane) in a mass ratio of 10:1, and stir and degas in a mixer for 4 minutes to obtain a PDMS mixture, which is ready for use;
  • the PDMS mixture in A2 is poured on an acrylic plate with velvet arrowroot leaves, placed in a vacuum environment for curing for 20h, and the cured PDMS is peeled off from the velvet arrowroot leaves to obtain a side with velvet arrowroot leaves.
  • the mold with the opposite structure of the slightly convex cone on the blade surface;
  • A4 Put the mold obtained in A3 into a plasma cleaning machine and treat it with oxygen plasma for 3 minutes, then immerse the mold in an aqueous ethanol solution with a mass concentration of 80%, and then put it in a vacuum drying box and dry it at 70 °C for 2 hours. Blow dry the mold with nitrogen;
  • step S4 Drop the PDMS mixture in A2 into the surface of the mold treated in step S4, which has a structure opposite to that of the surface of the velvet arrowroot blade, spin coating at a speed of 400r/min for 10-20s; then put in Heat and cure in an oven with a temperature of 90°C for 30 minutes, and remove the cured PDMS from the mold to obtain a PDMS film with the same structural surface as the surface of the velvety arrowroot blade surface microconvex cone;
  • A6 Use PET double-sided tape to attach the PDMS film in A5 to a stainless steel template (100-300 ⁇ m in thickness) with a plurality of through holes with different apertures.
  • the PDMS film has a slightly convex surface similar to that of velvet arrowroot leaves.
  • the surface of the cone with the same structure is adhered to the stainless steel template; the stainless steel template is placed in the vacuum adsorption device, the vacuum adsorption is turned on, the PDMS film will form a concave shape at the through hole due to the pressure difference between the upper and lower surfaces; the PDMS in A2
  • the mixture was dropped into the PDMS film to form the concave side surface, spin-coated at a speed of 400r/min for 10s; then heated and cured at 60°C for 15min with an infrared lamp, and then the PDMS film was placed in an oven with a temperature of 90°C to bake again
  • the PDMS was completely cured in 50min, and finally the PDMS film was peeled off from the stainless steel template;
  • A7 Add AgNWs (Jiangsu Xianfeng Nanomaterials Technology Co., Ltd., XF-J02) into absolute ethanol, and ultrasonically disperse for 15min to obtain AgNWs dispersion liquid, which is for subsequent use; wherein the mass ratio of AgNWs to absolute ethanol is 1:5;
  • A8 Put the PDMS film in A6 into a plasma cleaning machine and treat it with oxygen plasma for 4 minutes, and use a spray gun to spray the AgNWs dispersion on the surface of the PDMS film with the micro-convex cone structure on the surface of the velvet arrowroot leaf until the PDMS film The surface resistance value was 20 ⁇ . Finally, it was annealed in an oven with a temperature of 90 °C for 50 min, so that the solvent in the AgNWs dispersion was completely evaporated, and the biomimetic microarray flexible electrode was prepared.
  • the embodiment of the present application also provides a method for preparing an ion gel dielectric layer, comprising the following steps:
  • the above mixed solution was spin-coated on the glass at a speed of 400 r/min for 50 s, and then placed in a vacuum drying oven with a temperature of 50 °C for 2 h, and the mixture on the glass was peeled off to obtain an ionogel dielectric layer.
  • biomimetic microarray flexible electrode and the ionogel dielectric layer prepared in the above embodiment 1 are assembled into a flexible pressure sensor, and the specific method is as follows:
  • Two biomimetic microarray flexible electrodes were prepared according to the method in Example 1 above, and wires were drawn from the two biomimetic microarray flexible electrodes, and the wires and electrodes were bonded with conductive silver paste, and then placed in a 90°C oven to cure for 50 minutes;
  • the ionogel dielectric layer prepared in the above Example 1 is placed between two biomimetic microarray flexible electrodes 6, and then the biomimetic microarray flexible electrodes 6 are sealed around with polyimide tape, that is, the assembly of the flexible pressure sensor is completed. .
  • the surface morphology of the biomimetic microarray flexible electrode prepared in the above Example 1 is shown in Figure 7. It can be seen from Figure 7 that a large number of micron-scale cone-shaped structures are uniformly distributed on the millimeter-scale hemispherical array.
  • the diameter of each cone is about 15-25 ⁇ m and the height is about 20-30 ⁇ m.
  • the flexible pressure sensor has high sensitivity in the range of 0-90KPa, which ensures that the sensor can accurately sense pressure in a large measurement range, especially in the lower pressure area, the sensitivity is as high as 37.5KPa -1 , which can Sensing extremely weak pressure signals such as pulse vibration greatly expands the application range of flexible sensors.
  • the flexible pressure sensor can continuously collect the human pulse waveform, and the main wave (P wave), tidal wave (T wave) and dichotomous wave (D wave) in each waveform can be clearly identified , from which important physiological information can be extracted for evaluating the health status of the human body.
  • P wave main wave
  • T wave tidal wave
  • D wave dichotomous wave
  • the flexible pressure sensor assembled in the above Example 1 was tested to detect the pressure on the sole of the human body.
  • the flexible sensor was applied to the heel of the volunteer with medical tape, and the LCR source meter was used to detect the output signal of the human body during walking. , the results are shown in Figure 10.

Abstract

A bionic microarray flexible electrode (6) and a preparation method therefor, and a flexible pressure sensor, the preparation method for a flexible electrode (6) comprising the following steps: providing a plant leaf; mixing a PDMS prepolymer with a curing agent so as to obtain a PDMS mixture (2); pouring the PDMS mixture (2) onto the plant leaf, and removing the cured PDMS so as to obtain a mold (3); attaching the mold (3) onto a template (5), and starting vacuum adsorption; and preparing an AgNWs dispersion liquid and spraying same onto the mold (3), and performing annealing treatment. By means of the preparation method for a flexible electrode (6), a mold (3) is obtained by means of preparation by using, as a template, a plant leaf which has specific micron-scale conical array structures on the surface; and in combination with millimeter-level semicircular convex arrays which are formed by means of vacuum adsorption, a three-dimensional array structure of different sizes ranging from a micron level to a millimeter level is formed, and a microarray flexible electrode (6) provided with the structure is thus formed. Therefore, a sensor has good response characteristics to different levels of pressure and has a broadened measurement range.

Description

一种仿生微阵列柔性电极及其制备方法、柔性压力传感器A biomimetic microarray flexible electrode and preparation method thereof, and flexible pressure sensor 技术领域technical field
本发明涉及柔性可穿戴健康电子设备技术领域，尤其涉及一种仿生微阵列柔性电极及其制备方法、柔性压力传感器。The invention relates to the technical field of flexible wearable health electronic devices, in particular to a biomimetic microarray flexible electrode, a preparation method thereof, and a flexible pressure sensor.
背景技术Background technique
近年来，5G通讯技术的快速发展极大的促进了物联网与智能终端的交叉融合，而作为其核心部件之一的柔性压力传感器，在医疗健康、运动检测与矫正等方面发挥着越来越重要的作用。柔性压力传感器具有适形性好，轻薄便携等特点。基于柔性压力传感器的医疗可穿戴设备可以集成到衣服、配件或直接贴敷于皮肤表面，动态收集人体生理信息，用于反馈判断人体的健康状况。柔性压力传感器可根据使用场景任意贴附于不规则的三维物体表面进行信号检测，如贴敷于喉咙处监测声带的振动，可以实现不能说话的患者声音再现，贴敷在人体腹部对人体呼吸强度和频率进行监测等。In recent years, the rapid development of 5G communication technology has greatly promoted the cross-integration of the Internet of Things and intelligent terminals. As one of its core components, the flexible pressure sensor plays an increasingly important role in medical health, motion detection and correction, etc. important role. The flexible pressure sensor has the characteristics of good conformability, lightness and portability. Medical wearable devices based on flexible pressure sensors can be integrated into clothing, accessories, or directly attached to the skin surface to dynamically collect human physiological information for feedback and judgment of human health. The flexible pressure sensor can be arbitrarily attached to the surface of an irregular three-dimensional object for signal detection according to the usage scene. For example, it can be attached to the throat to monitor the vibration of the vocal cords. and frequency monitoring, etc.
电学性能优异的柔性压力传感器主要包括高性能柔性基底电极和敏感材料，结合特殊的结构实现。目前，柔性压力传感器多采用如硅片刻蚀，气相沉积和高分率3D打印等工艺复杂，设备昂贵的高耗能的方法制备，其高昂的制造成本限制了它在现实生活中的发展和应用；另一方面，绝大部分柔性压力传感器灵敏度不高，测量范围窄，对微弱生理信号无法积极识别，这些不足严重制约了柔性压力传感器对各种复杂生理信号的综合分析检测。Flexible pressure sensors with excellent electrical properties mainly include high-performance flexible substrate electrodes and sensitive materials, which are realized in combination with special structures. At present, flexible pressure sensors are mostly prepared by methods such as silicon wafer etching, vapor deposition, and high-resolution 3D printing, which are complicated in process, expensive and energy-intensive. The high manufacturing cost limits its development and application in real life. On the other hand, most flexible pressure sensors have low sensitivity, narrow measurement range, and cannot actively identify weak physiological signals. These shortcomings seriously restrict the comprehensive analysis and detection of various complex physiological signals by flexible pressure sensors.
基于目前的柔性压力传感器存在的技术问题，有必要对此进行改进。Based on the technical problems existing in the current flexible pressure sensor, it is necessary to improve this.
发明内容SUMMARY OF THE INVENTION
有鉴于此，本发明提出了一种仿生微阵列柔性电极及其制备方法、柔性压力传感器，以解决或部分解决现有技术中存在的技术问题。In view of this, the present invention proposes a bionic microarray flexible electrode, a preparation method thereof, and a flexible pressure sensor to solve or partially solve the technical problems existing in the prior art.
第一方面，本发明提供了一种仿生微阵列柔性电极的制备方法，包括以下步骤：In a first aspect, the present invention provides a preparation method of a biomimetic microarray flexible electrode, comprising the following steps:
提供一具有叶面纹理的植物叶片；providing a plant leaf with foliar texture;
将PDMS预聚物与固化剂混合后得到PDMS混合物，备用；After the PDMS prepolymer is mixed with the curing agent, the PDMS mixture is obtained, which is for subsequent use;
将所述PDMS混合物浇注在所述植物叶片上，使PDMS固化，将固化后的PDMS从所述植物叶片上取出得到表面与植物叶片表面相反的模具；The PDMS mixture is poured on the plant leaves, the PDMS is cured, and the cured PDMS is taken out from the plant leaves to obtain a mold whose surface is opposite to the surface of the plant leaves;
将所述模具的与植物叶片表面相反的表面贴附在设有多个通孔的模板上，将所述模板置于真空吸附装置内，开启真空吸附，将模具与模板分离；The surface of the mold opposite to the surface of the plant leaf is attached to the template provided with a plurality of through holes, the template is placed in a vacuum adsorption device, the vacuum adsorption is turned on, and the mold is separated from the template;
配制AgNWs分散液，将所述AgNWs分散液喷涂至经过真空吸附后的模具上，经过退火处理，即得仿生微阵列柔性电极。AgNWs dispersion liquid is prepared, the AgNWs dispersion liquid is sprayed onto the mold after vacuum adsorption, and annealed to obtain a biomimetic microarray flexible electrode.
在以上技术方案的基础上，优选的，所述的仿生微阵列柔性电极的制备方法，将所述模具的与植物叶片表面相反的表面贴附在设有多个通孔的模板上之前还包括：将所述PDMS混合物滴入模具的与植物叶片表面相反的表面，再经过旋涂，固化，再将固化后的PDMS从模具中取下得到表面呈微圆锥体的PDMS薄膜；再将所述PDMS薄膜的呈微圆锥体的表面贴附在设有多个通孔的模板上，再经过真空吸附，分离PDMS薄膜与模板；再将所述AgNWs分散液喷涂至经过真空吸附后的PDMS薄膜上，经过退火处理，即得仿生微阵列柔性电极。On the basis of the above technical solutions, preferably, the preparation method of the biomimetic microarray flexible electrode further comprises, before attaching the surface of the mold opposite to the surface of the plant leaf on the template provided with a plurality of through holes : drop the PDMS mixture into the surface of the mold opposite to the surface of the plant leaf, spin-coat, cure, and remove the cured PDMS from the mold to obtain a PDMS film with a micro-cone surface; The micro-conical surface of the PDMS film is attached to the template with a plurality of through holes, and then vacuum adsorption is performed to separate the PDMS film and the template; and then the AgNWs dispersion is sprayed onto the PDMS film after vacuum adsorption. , after annealing treatment, the biomimetic microarray flexible electrode is obtained.
进一步优选的，所述的仿生微阵列柔性电极的制备方法，再将所述AgNWs分散液喷涂至经过真空吸附后的PDMS薄膜上之前还包括：将所述PDMS混合物滴入PDMS薄膜的远离呈微圆锥体的表面，再经过旋涂，并使PDMS固化，再将经过固化的PDMS薄膜与模板分离；再将所述AgNWs分散液喷涂至经过固化的PDMS薄膜上，经过退火处理，即得仿生微阵列柔性电极。Further preferably, the preparation method of the biomimetic microarray flexible electrode, before spraying the AgNWs dispersion on the PDMS film after vacuum adsorption, further comprises: dropping the PDMS mixture into the PDMS film far away from the PDMS film. The surface of the cone is spin-coated, and the PDMS is cured, and then the cured PDMS film is separated from the template; the AgNWs dispersion is then sprayed onto the cured PDMS film, and annealed to obtain a biomimetic microarray. Array of flexible electrodes.
进一步优选的，所述的仿生微阵列柔性电极的制备方法，将所述PDMS混合物滴入模具的与植物叶片表面相反的表面之前还包括：将所述模具置于醇溶液中进行钝化。Further preferably, the preparation method of the biomimetic microarray flexible electrode, before dropping the PDMS mixture into the surface of the mold opposite to the surface of the plant leaf, further comprises: placing the mold in an alcohol solution for passivation.
进一步优选的，所述的仿生微阵列柔性电极的制备方法，将所述PDMS混合物滴入模具的与植物叶片表面相反的表面，再经过旋涂，固化，其中，旋涂具体为：以300～500r/min的转速旋涂10～20s；固化具体为：于80～100℃下固化20～40min。Further preferably, in the preparation method of the biomimetic microarray flexible electrode, the PDMS mixture is dropped into the surface of the mold opposite to the surface of the plant leaf, and then spin-coated and cured. Spin coating at 500r/min for 10-20s; curing is as follows: curing at 80-100℃ for 20-40min.
进一步优选的，所述的仿生微阵列柔性电极的制备方法，将所述PDMS混合物滴入PDMS薄膜的远离呈微圆锥体一侧的表面，再经过旋涂，并使PDMS固化，其中，旋涂具体为：以300～500r/min的转速旋涂8～12s；固化具体为：先于红外线灯下加热固化10～20min，再于80～100℃的烘箱中加热40～60min。Further preferably, in the preparation method of the biomimetic microarray flexible electrode, the PDMS mixture is dropped into the surface of the PDMS film away from the side of the microcone, and then spin-coated, and the PDMS is cured, wherein the spin-coating is performed. Specifically: spin coating at a speed of 300-500r/min for 8-12s; curing is as follows: first heating and curing under an infrared lamp for 10-20min, and then heating in an oven at 80-100°C for 40-60min.
在以上技术方案的基础上，优选的，所述的仿生微阵列柔性电极的制备方法，所述AgNWs分散液的制备方法为：将AgNWs加入至无水乙醇中，超声分散，即得AgNWs分散液；On the basis of the above technical solutions, preferably, in the preparation method of the biomimetic microarray flexible electrode, the preparation method of the AgNWs dispersion is as follows: adding the AgNWs into anhydrous ethanol and ultrasonically dispersing to obtain the AgNWs dispersion ;
和/或，所述退火处理具体为：于80～100℃的烘箱中退火处理40～60min。And/or, the annealing treatment is specifically: annealing treatment in an oven at 80-100° C. for 40-60 minutes.
第二方面，本发明还提供了一种仿生微阵列柔性电极，采用所述的制备方法制备得到。In a second aspect, the present invention also provides a biomimetic microarray flexible electrode, which is prepared by the preparation method.
第三方面，本发明还提供了一种柔性压力传感器，包括：In a third aspect, the present invention also provides a flexible pressure sensor, comprising:
一对所述的仿生微阵列柔性电极；a pair of the bionic microarray flexible electrodes;
离子凝胶介电层，位于一对所述的仿生微阵列柔性电极之间。The ion gel dielectric layer is located between a pair of the flexible electrodes of the biomimetic microarray.
在以上技术方案的基础上，优选的，所述的柔性压力传感器，所述离子凝胶介电层的制备方法包括以下步骤：On the basis of the above technical solutions, preferably, the flexible pressure sensor, the preparation method of the ion gel dielectric layer comprises the following steps:
将PVDF-HFP加入至丙酮中，搅拌均匀后，再加入离子液体，继续搅拌得到混合溶液；Add PVDF-HFP into acetone, stir evenly, then add ionic liquid and continue stirring to obtain a mixed solution;
将混合溶液涂覆在基底上，然后退火，经过剥离即得离子凝胶介电层。The mixed solution is coated on the substrate, then annealed, and the ion gel dielectric layer is obtained by peeling off.
本发明的一种仿生微阵列柔性电极和柔性压力传感器相对于现有技术具有以下有益效果：The biomimetic microarray flexible electrode and flexible pressure sensor of the present invention have the following beneficial effects compared to the prior art:
(1)本发明的仿生微阵列柔性电极的制备方法，以表面具有特有的微米级锥型阵列结构的植物叶片为模板，制备得到模具，同时结合真空吸附形成的毫米 级半圆凸起阵列，形成具有微米至毫米等不同尺寸的三维阵列结构，具有该结构的微阵列柔性电极，使得传感器对对不同量级的压力具有良好的响应特性，测量范围大大拓宽；(1) In the preparation method of the biomimetic microarray flexible electrode of the present invention, a plant leaf with a unique micron-scale conical array structure on the surface is used as a template to prepare a mold, and a millimeter-scale semicircular convex array formed by vacuum adsorption is combined to form It has a three-dimensional array structure with different sizes such as micrometers to millimeters. The microarray flexible electrodes with this structure make the sensor have good response characteristics to pressures of different magnitudes, and the measurement range is greatly expanded;
(2)本发明的柔性压力传感器，对压力的响应是由不同尺寸的微阵列结构的柔性电极变化和离子凝胶层的界面电容变化共同作用完成，由于本申请的离子凝胶层超高的比电容，使得该压力传感器在面对外界压力时比普通电容式的柔性传感器有着更显著的电容变化，使得该传感器具有极高的灵敏度和响应性；同时本申请的压力传感器结构简单，制作步骤容易，极大的降低了制作成本和加工难度。(2) The response of the flexible pressure sensor of the present invention to the pressure is completed by the changes of the flexible electrodes of the microarray structures of different sizes and the change of the interfacial capacitance of the ion gel layer. The specific capacitance makes the pressure sensor have a more significant capacitance change than ordinary capacitive flexible sensors in the face of external pressure, so that the sensor has extremely high sensitivity and responsiveness; at the same time, the pressure sensor of the present application has a simple structure and manufacturing steps. It is easy, which greatly reduces the production cost and processing difficulty.
附图说明Description of drawings
为了更清楚地说明本发明实施例或现有技术中的技术方案，下面将对实施例或现有技术描述中所需要使用的附图作简单的介绍。显而易见地，下面描述中的附图仅仅是本发明的一些实施例，对于本领域普通技术人员来讲，在不付出创造性劳动的前提下，还可以根据这些附图获得其他的附图。In order to illustrate the embodiments of the present invention or the technical solutions in the prior art more clearly, the following briefly introduces the accompanying drawings that are required to be used in the description of the embodiments or the prior art. Obviously, the drawings in the following description are only some embodiments of the present invention, and for those of ordinary skill in the art, other drawings can also be obtained from these drawings without creative effort.
图1为本发明的一种仿生微阵列柔性电极的制备方法，其中一个实施例中在天鹅绒竹芋叶片表面浇注PDMS混合物的示意图；Fig. 1 is the preparation method of a kind of biomimetic microarray flexible electrode of the present invention, wherein in one embodiment, the schematic diagram of pouring PDMS mixture on the surface of velvet arrowroot leaves;
图2为本发明的一种仿生微阵列柔性电极的制备方法，其中一个实施例中在形成的模具表面继续旋涂PDMS混合物的示意图；2 is a schematic diagram of a preparation method of a biomimetic microarray flexible electrode of the present invention, wherein in one embodiment, the PDMS mixture is continuously spin-coated on the surface of the formed mold;
图3为本发明的一种仿生微阵列柔性电极的制备方法，其中一个实施例中将PDMS薄膜粘附在设有多个通孔的模板的示意图；3 is a schematic diagram of a method for preparing a bionic microarray flexible electrode of the present invention, wherein in one embodiment, a PDMS film is adhered to a template provided with a plurality of through holes;
图4为本发明的一种仿生微阵列柔性电极的制备方法，其中一个实施例中仿生微阵列柔性电极的结构示意图；4 is a method for preparing a biomimetic microarray flexible electrode according to the present invention, and a schematic structural diagram of a biomimetic microarray flexible electrode in one embodiment;
图5为本发明的柔性压力传感器的结构示意图；5 is a schematic structural diagram of the flexible pressure sensor of the present invention;
图6为本发明的柔性压力传感器，其中一个实施例中在基底上制备得到离子凝胶介电层的示意图；6 is a schematic diagram of the flexible pressure sensor of the present invention, wherein an ionogel dielectric layer is prepared on a substrate in one embodiment;
图7为本发明实施例1中制备得到的仿生微阵列柔性电极的表面形貌图；FIG. 7 is a surface topography diagram of the biomimetic microarray flexible electrode prepared in Example 1 of the present invention;
图8为本发明实施例1中组装而成的柔性压力传感器的灵敏度和响应曲线 图；Fig. 8 is the sensitivity and response curve diagram of the flexible pressure sensor assembled in embodiment 1 of the present invention;
图9为本发明实施例1中组装而成的柔性压力传感器的对人体脉搏进行检测的曲线图；FIG. 9 is a graph showing the detection of human pulse of the flexible pressure sensor assembled in Embodiment 1 of the present invention;
图10为本发明实施例1中组装而成的柔性压力传感器的对人体足底压力进行检测曲线图。FIG. 10 is a graph showing the detection of the pressure on the sole of the human body by the flexible pressure sensor assembled in Embodiment 1 of the present invention.
具体实施方式Detailed ways
下面将结合本发明实施方式，对本发明实施方式中的技术方案进行清楚、完整的描述，显然，所描述的实施方式仅仅是本发明一部分实施方式，而不是全部的实施方式。基于本发明中的实施方式，本领域普通技术人员在没有做出创造性劳动前提下所获得的所有其他实施方式，都属于本发明保护的范围。The technical solutions in the embodiments of the present invention will be clearly and completely described below in conjunction with the embodiments of the present invention. Obviously, the described embodiments are only a part of the embodiments of the present invention, but not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by persons of ordinary skill in the art without creative efforts shall fall within the protection scope of the present invention.
本发明提供了一种仿生微阵列柔性电极的制备方法，包括以下步骤：The invention provides a preparation method of a bionic microarray flexible electrode, comprising the following steps:
S1、提供一具有叶面纹理的植物叶片；S1, provide a plant leaf with foliar texture;
S2、将PDMS预聚物与固化剂混合后得到PDMS混合物，备用；S2, the PDMS mixture is obtained after mixing the PDMS prepolymer and the curing agent, and is for subsequent use;
S3、将PDMS混合物浇注在植物叶片上，使PDMS固化，将固化后的PDMS从植物叶片上取出得到表面与植物叶片表面相反的模具；S3, pouring the PDMS mixture on the plant leaves to solidify the PDMS, and taking out the solidified PDMS from the plant leaves to obtain a mold with a surface opposite to the surface of the plant leaves;
S4、将模具的与植物叶片表面相反的表面贴附在设有多个通孔的模板上，将模板置于真空吸附装置内，开启真空吸附，将模具与模板分离；S4, attach the surface of the mold opposite to the surface of the plant leaf on the template provided with a plurality of through holes, place the template in a vacuum adsorption device, open the vacuum adsorption, and separate the mold from the template;
S5、配制AgNWs分散液，将AgNWs分散液喷涂至经过真空吸附后的模具上，经过退火处理，即得仿生微阵列柔性电极。S5, preparing an AgNWs dispersion, spraying the AgNWs dispersion onto the mold after vacuum adsorption, and annealing to obtain a bionic microarray flexible electrode.
需要说明的是，本申请的仿生微阵列柔性电极的制备方法中，具有叶面纹理的植物叶片指的是该植物叶片表面的纹理清楚、表面形成类似微米级微凸锥体阵列结构，比如该植物叶片包括天鹅绒竹芋叶片、西瓜皮、椒草叶片、窄叶柃叶片、肖竹芋叶片等；实际中可将植物叶片固定在基板上，然后浇注PDMS混合物，基板可采用亚克力板，显然采用其它的能起到载体作用的板体均可以；植物叶片可通过双面胶固定在基板上，对于天鹅绒竹芋叶片而言，将叶片正面固定在基板上；将PDMS混合物浇注在基板的植物叶片上，使PDMS固化，得到模具，该模具的一个表面具有与植物叶片表面微凸锥体阵列结构相反的阵 列结构，即形成微凹锥体结构；将模具的与植物叶片表面相反的表面贴附在设有多个通孔的模板上，即将模具的具有微凹锥体结构表面贴附在模板上，该模板上的通孔呈阵列设置，且通孔的直径大小可相同也可不相同，可采用PET基材双面胶将模具粘附在模板上，经过真空吸附后，模具由于上下表面之间的压力差会在模板的具有与植物叶片表面相反的表面且对应通孔区域形成毫米级类半圆形的凹状结构；然后再将AgNWs(银纳米线)分散液喷涂至经过真空吸附后的模具的具有与植物叶片表面相反的表面，即得仿生微阵列柔性电极。It should be noted that, in the preparation method of the biomimetic microarray flexible electrode of the present application, the plant leaf with leaf surface texture refers to the clear texture on the surface of the plant leaf, and the surface forms a similar micron-scale micro-convex cone array structure, such as this one. Plant leaves include velvet arrowroot leaves, watermelon rinds, pepper grass leaves, narrow-leaf tamarisk leaves, Xiao arrowroot leaves, etc. In practice, the plant leaves can be fixed on the substrate, and then the PDMS mixture is poured. The substrate can be acrylic plate, obviously using Other plates that can play the role of a carrier can be used; the plant leaves can be fixed on the substrate by double-sided tape, and for the velvet arrowroot leaves, the front of the leaf can be fixed on the substrate; the PDMS mixture is poured on the substrate. Plant leaves Then, the PDMS is cured to obtain a mold, one surface of the mold has an array structure opposite to the micro-convex pyramid array structure on the surface of the plant leaf, that is, a micro-concave pyramid structure is formed; the surface of the mold opposite to the surface of the plant leaf is attached On a template with a plurality of through holes, the surface of the mold with the micro-concave pyramid structure is attached to the template, the through holes on the template are arranged in an array, and the diameters of the through holes can be the same or different, and the diameter of the through holes can be the same or different. The mold is adhered to the template with PET substrate double-sided tape. After vacuum adsorption, the mold will form a millimeter-scale shape on the template with the opposite surface to the surface of the plant leaf and the corresponding through-hole area due to the pressure difference between the upper and lower surfaces of the mold. A semicircular concave structure; and then spraying the AgNWs (silver nanowire) dispersion to the surface of the mold after vacuum adsorption, which is opposite to the surface of the plant leaf, to obtain a biomimetic microarray flexible electrode.
在一些实施例中，将PDMS混合物浇注在植物叶片之前，还包括：将植物叶片置于去离子水中清洗2～4min，然后使用氮气吹干。In some embodiments, before pouring the PDMS mixture on the plant leaves, the method further includes: washing the plant leaves in deionized water for 2-4 minutes, and then blowing dry with nitrogen gas.
在一些实施例中，将PDMS预聚物与固化剂混合后得到PDMS混合物，其中，PDMS(聚二甲基硅氧烷)预聚物与固化剂的质量比为10:(1～3)，PDMS预聚物型号为道康宁184，固化剂为道康宁184。In some embodiments, the PDMS mixture is obtained after mixing the PDMS prepolymer and the curing agent, wherein the mass ratio of the PDMS (polydimethylsiloxane) prepolymer to the curing agent is 10:(1-3), The PDMS prepolymer model is Dow Corning 184, and the curing agent is Dow Corning 184.
在一些实施例中，将PDMS混合物浇注在植物叶片上之前还包括：将PDMS混合物放入搅拌机中搅拌脱气3～5分钟。In some embodiments, before pouring the PDMS mixture on the plant leaves, the method further comprises: putting the PDMS mixture into a blender and stirring and degassing for 3-5 minutes.
在一些实施例中，将模具的与植物叶片表面相反的表面贴附在设有多个通孔的模板上之前还包括：将PDMS混合物滴入模具的与植物叶片表面相反的表面，再经过旋涂，固化，再将固化后的PDMS从模具中取下得到表面呈微圆锥体的PDMS薄膜；再将PDMS薄膜的呈微圆锥体的表面贴附在设有多个通孔的模板上，再经过真空吸附，分离PDMS薄膜与模板；再将AgNWs分散液喷涂至经过真空吸附后的PDMS薄膜上，经过退火处理，即得仿生微阵列柔性电极。在本申请实施例中，将PDMS混合物滴入模具表面，固化后得到PDMS薄膜，该PDMS薄膜的表面呈微圆锥体，具体的，该PDMS薄膜的表面具有与植物叶片相同的表面微凸锥体阵列结构；喷涂时，将AgNWs分散液喷涂至PDMS薄膜的呈微圆锥体的表面。In some embodiments, before attaching the surface of the mold opposite to the surface of the plant leaves on the template provided with the plurality of through holes, the method further includes: dropping the PDMS mixture into the surface of the mold opposite to the surface of the plant leaves, and then rotating the mold. Coating, curing, and then removing the cured PDMS from the mold to obtain a PDMS film with a micro-cone surface; then attaching the micro-cone surface of the PDMS film to a template with multiple through holes, and then After vacuum adsorption, the PDMS film and the template were separated; then, the AgNWs dispersion was sprayed onto the PDMS film after vacuum adsorption, and annealed to obtain a biomimetic microarray flexible electrode. In the examples of the present application, the PDMS mixture was dropped onto the surface of the mold, and after curing, a PDMS film was obtained. The surface of the PDMS film was in the shape of a microcone. Specifically, the surface of the PDMS film had the same surface microconvex cone as the plant leaf. Array structure; when spraying, the AgNWs dispersion was sprayed onto the surface of the PDMS film in the form of microcones.
在一些实施例中，再将AgNWs分散液喷涂至经过真空吸附后的PDMS薄膜上之前还包括：将PDMS混合物滴入PDMS薄膜的远离呈微圆锥体一侧的表面，再经过旋涂，并使PDMS固化，再将经过固化的PDMS薄膜与模板分离；再将AgNWs分散液喷涂至经过固化的PDMS薄膜上，经过退火处理， 即得仿生微阵列柔性电极。在本申请实施例中，将PDMS混合物再次滴入PDMS薄膜表面，在喷涂AgNWs分散液，这样制备得到的仿生微阵列柔性电极形成多层次上下极板结构，该结构对不同量级的压力具有良好的响应特性。In some embodiments, before spraying the AgNWs dispersion on the PDMS film after vacuum adsorption, the method further includes: dropping the PDMS mixture onto the surface of the PDMS film away from the side of the microcone, spin coating, and making The PDMS is cured, and then the cured PDMS film is separated from the template; the AgNWs dispersion is sprayed onto the cured PDMS film, and annealed to obtain a biomimetic microarray flexible electrode. In the examples of the present application, the PDMS mixture was dropped again on the surface of the PDMS film, and the AgNWs dispersion was sprayed. The biomimetic microarray flexible electrodes prepared in this way formed a multi-level upper and lower plate structure, which has good resistance to pressures of different magnitudes. response characteristics.
在一些实施例中，将PDMS混合物滴入模具的与植物叶片表面相反的表面之前还包括：将模具置于醇溶液中进行钝化。醇溶液为无水乙醇溶液；具体的，实际中，先将模具放入等离子清洗机中用氧气等离子体处理2～4min，然后将模具浸没在无水乙醇溶液中，再置入真空干燥箱于70～80℃下干燥1～3h，取出后用氮气吹干模具；通过钝化使模具表面疏水，这样便于使PDMS薄膜从模具中取出。In some embodiments, prior to dropping the PDMS mixture onto the surface of the mold opposite to the surface of the plant leaves further comprises: placing the mold in an alcohol solution for passivation. The alcohol solution is an anhydrous ethanol solution; specifically, in practice, the mold is first placed in a plasma cleaning machine and treated with oxygen plasma for 2 to 4 minutes, then the mold is immersed in an anhydrous ethanol solution, and then placed in a vacuum drying box at Dry at 70-80°C for 1-3 hours, and blow dry the mold with nitrogen after taking it out; the surface of the mold is made hydrophobic by passivation, which facilitates the removal of the PDMS film from the mold.
在一些实施例中，将PDMS混合物滴入模具的与植物叶片表面相反的表面，再经过旋涂，固化，其中，旋涂具体为：以300～500r/min的转速旋涂10～20s；固化具体为：于80～100℃下固化20～40min。In some embodiments, the PDMS mixture is dropped into the surface of the mold opposite to the surface of the plant leaf, and then spin-coated and cured, wherein the spin-coating is specifically: spin-coating at a rotational speed of 300-500 r/min for 10-20 s; curing; Specifically: curing at 80 to 100 ° C for 20 to 40 minutes.
在一些实施例中，将PDMS混合物滴入PDMS薄膜的远离呈微圆锥体的表面，再经过旋涂，并使PDMS固化，其中，旋涂具体为：以300～500r/min的转速旋涂8～12s；固化具体为：先于红外线灯下加热固化10～20min，再于80～100℃的烘箱中加热40～60min。In some embodiments, the PDMS mixture is dropped onto the surface of the PDMS film away from the micro-cone, and then spin-coated, and the PDMS is cured. ～12s; curing is as follows: firstly heating and curing under infrared lamp for 10～20min, and then heating in an oven at 80～100℃ for 40～60min.
在一些实施例中，AgNWs分散液的制备方法为：将AgNWs加入至无水乙醇中，超声分散，即得AgNWs分散液；In some embodiments, the preparation method of the AgNWs dispersion is as follows: adding the AgNWs into anhydrous ethanol, and ultrasonically dispersing to obtain the AgNWs dispersion;
和/或，所述退火处理具体为：于80～100℃的烘箱中退火处理40～60min。And/or, the annealing treatment is specifically: annealing treatment in an oven at 80-100° C. for 40-60 minutes.
具体的，AgNWs(银纳米线)与无水乙醇的质量比为1:(5～10)。Specifically, the mass ratio of AgNWs (silver nanowires) to absolute ethanol is 1:(5-10).
在一些实施例中，将AgNWs分散液喷涂至经过固化的PDMS薄膜表面，直到PDMS薄膜表面电阻电阻值为10～30Ω，在于80～100℃的烘箱中退火处理40～60min使得AgNWs分散液中溶剂完全蒸发，从而在PDMS薄膜表面形成AgNWs，并增加了AgNWs与PDMS薄膜之间的附着力。In some embodiments, the AgNWs dispersion is sprayed onto the surface of the cured PDMS film until the surface resistance value of the PDMS film is 10-30Ω, and annealed in an oven at 80-100°C for 40-60min to make the AgNWs dispersion in the solvent complete evaporation, thereby forming AgNWs on the surface of PDMS films and increasing the adhesion between AgNWs and PDMS films.
在一些实施例中，将AgNWs分散液喷涂至PDMS薄膜之前还包括：将PDMS薄膜放入等离子清洗机中用氧气等离子体处理3～5min，以提高PDMS薄膜表面的粘附能力。In some embodiments, before spraying the AgNWs dispersion onto the PDMS thin film, the method further includes: placing the PDMS thin film in a plasma cleaning machine and treating it with oxygen plasma for 3-5 minutes to improve the adhesion ability on the surface of the PDMS thin film.
图1～4显示了其中一个实施例中以天鹅绒竹芋叶片制备得到仿生微阵列柔性电极的示意图。其中，图1中为在天鹅绒竹芋叶片1表面浇注PDMS混合物2的示意图，固化后形成模具，天鹅绒竹芋叶片1表面微凸锥体阵列结构；图2为在形成的模具3表面继续旋涂PDMS混合物2，固化后，将PDMS从模具3上取出得到PDMS薄膜，显然该PDMS薄膜表面具有与模具3具有相反的结构，与天鹅绒竹芋叶片1表面具有相同的微结构，即上文提到的微圆锥体结构；图3为将PDMS薄膜4粘附在设有多个通孔51的模板5上，并经过真空吸附后在PDMS薄膜4上对应通孔51处形成凹状41，然后继续在PDMS薄膜4远离微圆锥体一侧的表面继续旋涂PDMS混合物2，待PDMS固化后，再将AgNWs分散液喷涂至PDMS薄膜4具有微圆锥体结构的表面，并在其表面形成AgNWs61，最终得到的仿生微阵列柔性电极6结构如图4所示。Figures 1-4 show schematic diagrams of biomimetic microarray flexible electrodes prepared from velvet arrowroot leaves in one of the embodiments. Wherein, in Fig. 1 is the schematic diagram of pouring PDMS mixture 2 on the surface of velvet arrowroot blade 1, after curing, a mold is formed, and the surface of velvet arrowroot blade 1 has a slightly convex cone array structure; Fig. 2 is a continuous spin coating on the surface of the formed mold 3 PDMS mixture 2, after curing, take out PDMS from mold 3 to obtain a PDMS film. Obviously, the surface of the PDMS film has an opposite structure to that of mold 3, and has the same microstructure as the surface of velvet arrowroot blade 1, which is mentioned above. Figure 3 shows that the PDMS film 4 is adhered to the template 5 with a plurality of through holes 51, and after vacuum adsorption, a concave shape 41 is formed on the PDMS film 4 corresponding to the through holes 51, and then continues on The surface of the PDMS film 4 away from the micro-cone side continues to spin-coat the PDMS mixture 2. After the PDMS is cured, the AgNWs dispersion is sprayed onto the surface of the PDMS film 4 with the micro-cone structure, and AgNWs61 are formed on the surface, and finally the obtained The structure of the biomimetic microarray flexible electrode 6 is shown in Figure 4.
基于同一发明构思，本发明还提供了一种柔性压力传感器，如图5所示，包括：Based on the same inventive concept, the present invention also provides a flexible pressure sensor, as shown in FIG. 5 , including:
一对由上述方法制备得到的仿生微阵列柔性电极6；A pair of biomimetic microarray flexible electrodes 6 prepared by the above method;
离子凝胶介电层7，位于一对仿生微阵列柔性电极6之间。The ion gel dielectric layer 7 is located between a pair of flexible electrodes 6 of a bionic microarray.
在一些实施例中，上述柔性压力传感器的组装方法，包括以下步骤：In some embodiments, the assembling method of the above-mentioned flexible pressure sensor includes the following steps:
在上述两个仿生微阵列柔性电极6的边缘分别引出导线，导线与电极使用导电银浆粘合，然后置于80～100℃烘箱中固化40-60min；再将离子凝胶介电层7置于两个仿生微阵列柔性电极6之间，再用聚酰亚胺胶带密封仿生微阵列柔性电极6四周，即完成柔性压力传感器的组装。Lead wires are drawn from the edges of the above two bionic microarray flexible electrodes 6 respectively, and the wires and electrodes are bonded with conductive silver paste, and then placed in an oven at 80-100°C for curing for 40-60min; then the ion gel dielectric layer 7 is placed on the Between the two biomimetic microarray flexible electrodes 6, the periphery of the biomimetic microarray flexible electrodes 6 is sealed with polyimide tape, and the flexible pressure sensor is assembled.
在一些实施例中，离子凝胶介电层7的制备方法包括以下步骤：In some embodiments, the preparation method of the ion gel dielectric layer 7 includes the following steps:
将PVDF-HFP(聚偏氟乙烯-六氟丙烯共聚物)加入至丙酮中，搅拌均匀后，再加入离子液体，继续搅拌得到混合溶液；Adding PVDF-HFP (polyvinylidene fluoride-hexafluoropropylene copolymer) into acetone, stirring evenly, then adding ionic liquid, and continuing to stir to obtain a mixed solution;
将混合溶液涂覆在基底上，然后退火，经过剥离即得离子凝胶介电层。The mixed solution is coated on the substrate, then annealed, and the ion gel dielectric layer is obtained by peeling off.
需要说明的是，本申请中离子液体为EMIM TFSI(1-乙基-3-甲基咪唑双三氟甲磺酰亚胺盐)，将PVDF-HFP(聚偏氟乙烯-六氟丙烯共聚物)加入至丙酮中，并在50～70℃下搅拌2～4h，使PVDF-HFP融化并均匀分散在丙酮溶剂中；接着再加入离子液体EMIM TFSI室温下搅拌1～2h得到混合溶液。It should be noted that the ionic liquid in this application is EMIM TFSI (1-ethyl-3-methylimidazole bis-trifluoromethanesulfonimide salt), and PVDF-HFP (polyvinylidene fluoride-hexafluoropropylene copolymer) ) was added to acetone, and stirred at 50 to 70 ° C for 2 to 4 hours, so that PVDF-HFP was melted and uniformly dispersed in the acetone solvent; then the ionic liquid EMIM TFSI was added and stirred at room temperature for 1 to 2 hours to obtain a mixed solution.
在一些实施例中，基底为玻璃基底，将上述混合溶液以300～500转/分的转速在玻璃基底上旋涂40～60秒，然后放入温度为40～60℃的真空干燥箱中退火1～3h，完全去除混合溶液中的溶剂，剥离后得到离子凝胶介电层。In some embodiments, the substrate is a glass substrate, the above mixed solution is spin-coated on the glass substrate at a speed of 300-500 r/min for 40-60 seconds, and then placed in a vacuum drying oven at a temperature of 40-60° C. for annealing For 1 to 3 hours, the solvent in the mixed solution is completely removed, and the ion gel dielectric layer is obtained after peeling off.
图6显示了在基底8上制备得到离子凝胶介电层7的示意图。FIG. 6 shows a schematic diagram of preparing the ion gel dielectric layer 7 on the substrate 8 .
本发明的仿生微阵列柔性电极的制备方法，以表面具有特有的微米级锥型阵列结构的植物叶片为模板，制备得到模具，再进一步利用该模具形成与植物叶片表面相同微结构阵列的PDMS薄膜，同时结合真空吸附形成的毫米级半圆凸起阵列，形成具有微米至毫米等不同尺寸的三维阵列结构，具有该结构的微阵列柔性电极，使得传感器对对不同量级的压力具有良好的响应特性，测量范围大大拓宽。In the preparation method of the biomimetic microarray flexible electrode of the present invention, a plant leaf with a unique micron-level cone array structure on the surface is used as a template to prepare a mold, and then the mold is further used to form a PDMS film with the same microstructure array as the surface of the plant leaf At the same time, combined with the millimeter-scale semicircular convex array formed by vacuum adsorption, a three-dimensional array structure with different sizes from micrometers to millimeters is formed. The microarray flexible electrodes with this structure make the sensor have good response characteristics to pressures of different magnitudes. , the measurement range is greatly expanded.
本发明的柔性压力传感器，对压力的响应是由不同尺寸的微阵列结构的柔性电极变化和离子凝胶层的界面电容变化共同作用完成，由于本申请的离子凝胶层超高的比电容，使得该压力传感器在面对外界压力时比普通电容式的柔性传感器有着更显著的电容变化，使得该传感器具有极高的灵敏度和响应性。In the flexible pressure sensor of the present invention, the response to pressure is completed by the changes of the flexible electrodes of the microarray structures of different sizes and the change of the interfacial capacitance of the ion gel layer. This makes the pressure sensor have a more significant capacitance change than ordinary capacitive flexible sensors when facing external pressure, so that the sensor has extremely high sensitivity and responsiveness.
以下进一步以具体的实施例说明本申请的仿生微阵列柔性电极和柔性压力传感器的制备方法。The following further describes the preparation methods of the biomimetic microarray flexible electrodes and flexible pressure sensors of the present application with specific examples.
实施例1Example 1
本申请实施例提供了一种仿生微阵列柔性电极的制备方法，包括以下步骤：The embodiment of the present application provides a preparation method of a biomimetic microarray flexible electrode, comprising the following steps:
A1、将天鹅绒竹芋叶片用去离子水冲洗3分钟并用氮气将表面吹干；接着，在亚克力板上粘上3M双面胶，将天鹅绒竹芋叶片正面朝上贴于亚克力板上；A1. Rinse the velvet arrowroot leaves with deionized water for 3 minutes and dry the surface with nitrogen; then, stick 3M double-sided tape on the acrylic board, and stick the velvet arrowroot leaves face up on the acrylic board;
A2、将PDMS预聚物poly(dimethyl-methylvinylsiloxane)与固化剂poly(dimethyl-methylhydrogenosiloxane)按照10:1质量比混合，并搅拌机中搅拌脱气4min，得到PDMS混合物，备用；A2. Mix the PDMS prepolymer poly(dimethyl-methylvinylsiloxane) and the curing agent poly(dimethyl-methylhydrogenosiloxane) in a mass ratio of 10:1, and stir and degas in a mixer for 4 minutes to obtain a PDMS mixture, which is ready for use;
A3、将A2中的PDMS混合物浇筑在贴有天鹅绒竹芋叶片的亚克力板上，置于真空环境中固化20h，将固化后的PDMS从天鹅绒竹芋叶片上揭下，得到一面具有与天鹅绒竹芋叶片表面微凸锥体相反结构的模具；A3. The PDMS mixture in A2 is poured on an acrylic plate with velvet arrowroot leaves, placed in a vacuum environment for curing for 20h, and the cured PDMS is peeled off from the velvet arrowroot leaves to obtain a side with velvet arrowroot leaves. The mold with the opposite structure of the slightly convex cone on the blade surface;
A4、将A3中得到的模具置于等离子清洗机中用氧气等离子体处理3min，然后将模具浸没在质量浓度为80％乙醇水溶液中，然后置入真空干燥箱于70℃下干燥2h，取出后用氮气吹干模具；A4. Put the mold obtained in A3 into a plasma cleaning machine and treat it with oxygen plasma for 3 minutes, then immerse the mold in an aqueous ethanol solution with a mass concentration of 80%, and then put it in a vacuum drying box and dry it at 70 °C for 2 hours. Blow dry the mold with nitrogen;
A5、将A2中的PDMS混合物滴入经过步骤S4处理后的模具的具有与天鹅绒竹芋叶片表面微凸锥体相反的结构的表面，以400r/min的转速旋涂10-20s；之后放入温度为90℃的烘箱中加热固化30min，从模具中取下固化后的PDMS，即得到具有与天鹅绒竹芋叶片表面微凸锥体相同结构表面的PDMS薄膜；A5. Drop the PDMS mixture in A2 into the surface of the mold treated in step S4, which has a structure opposite to that of the surface of the velvet arrowroot blade, spin coating at a speed of 400r/min for 10-20s; then put in Heat and cure in an oven with a temperature of 90°C for 30 minutes, and remove the cured PDMS from the mold to obtain a PDMS film with the same structural surface as the surface of the velvety arrowroot blade surface microconvex cone;
A6、将A5中的PDMS薄膜采用PET双面胶贴附在设有多个不同孔径通孔的不锈钢模板上(厚度为100～300μm)，其中，PDMS薄膜的具有与天鹅绒竹芋叶片表面微凸锥体相同结构的表面粘附于不锈钢模板上；将不锈钢模板置于真空吸附装置内，开启真空吸附，PDMS薄膜由于上下表面之间的压力差会在通孔处形成凹状；将A2中的PDMS混合物滴入PDMS薄膜形成凹状一侧的表面，以400r/min的转速旋涂10s；然后采用红外线灯于60℃下加热固化15min，再将PDMS薄膜放入温度为90℃的烘箱中再次烘烤50min完全固化PDMS，最后将PDMS薄膜从不锈钢模板剥离；A6. Use PET double-sided tape to attach the PDMS film in A5 to a stainless steel template (100-300 μm in thickness) with a plurality of through holes with different apertures. The PDMS film has a slightly convex surface similar to that of velvet arrowroot leaves. The surface of the cone with the same structure is adhered to the stainless steel template; the stainless steel template is placed in the vacuum adsorption device, the vacuum adsorption is turned on, the PDMS film will form a concave shape at the through hole due to the pressure difference between the upper and lower surfaces; the PDMS in A2 The mixture was dropped into the PDMS film to form the concave side surface, spin-coated at a speed of 400r/min for 10s; then heated and cured at 60°C for 15min with an infrared lamp, and then the PDMS film was placed in an oven with a temperature of 90°C to bake again The PDMS was completely cured in 50min, and finally the PDMS film was peeled off from the stainless steel template;
A7、将AgNWs(江苏先丰纳米材料科技有限公司，XF-J02)加入至无水乙醇中，超声分散15min，得到AgNWs分散液，备用；其中AgNWs与无水乙醇的质量比为1:5；A7. Add AgNWs (Jiangsu Xianfeng Nanomaterials Technology Co., Ltd., XF-J02) into absolute ethanol, and ultrasonically disperse for 15min to obtain AgNWs dispersion liquid, which is for subsequent use; wherein the mass ratio of AgNWs to absolute ethanol is 1:5;
A8、将A6中的PDMS薄膜置于等离子清洗机中用氧气等离子体处理4min，使用喷枪将AgNWs分散液喷涂在PDMS薄膜的具有与天鹅绒竹芋叶片表面微凸锥体结构的表面，直到PDMS薄膜表面电阻电阻值为20Ω，最后将其放入温度为90℃的烘箱中退火处理50min，使得AgNWs分散液中溶剂完全蒸发，即制备得到仿生微阵列柔性电极。A8. Put the PDMS film in A6 into a plasma cleaning machine and treat it with oxygen plasma for 4 minutes, and use a spray gun to spray the AgNWs dispersion on the surface of the PDMS film with the micro-convex cone structure on the surface of the velvet arrowroot leaf until the PDMS film The surface resistance value was 20Ω. Finally, it was annealed in an oven with a temperature of 90 °C for 50 min, so that the solvent in the AgNWs dispersion was completely evaporated, and the biomimetic microarray flexible electrode was prepared.
本申请实施例还提供了一种离子凝胶介电层的制备方法，包括以下步骤：The embodiment of the present application also provides a method for preparing an ion gel dielectric layer, comprising the following steps:
将PVDF-HFP(Sigma-Aldrich,427179-100g)与丙酮混合，然后于60℃下搅拌3h，然后加入EMIM TFSI，继续搅拌均匀，得到混合溶液；其中EMIM TFSI(aladdin，E101506-5g)、PVDF-HFP和丙酮的质量比为1:1.5:10.5；Mix PVDF-HFP (Sigma-Aldrich, 427179-100g) with acetone, then stir at 60°C for 3h, then add EMIM TFSI and continue stirring to obtain a mixed solution; wherein EMIM TFSI (aladdin, E101506-5g), PVDF -The mass ratio of HFP and acetone is 1:1.5:10.5;
将上述混合溶液以400r/min的转速在玻璃上旋涂50s，然后放入温度为50℃的真空干燥箱中退火2h，将玻璃上的混合物剥离后即得离子凝胶介电层。The above mixed solution was spin-coated on the glass at a speed of 400 r/min for 50 s, and then placed in a vacuum drying oven with a temperature of 50 °C for 2 h, and the mixture on the glass was peeled off to obtain an ionogel dielectric layer.
将上述实施例1中制备得到的仿生微阵列柔性电极和离子凝胶介电层组装成柔性压力传感器，具体方法为：The biomimetic microarray flexible electrode and the ionogel dielectric layer prepared in the above embodiment 1 are assembled into a flexible pressure sensor, and the specific method is as follows:
按照上述实施例1中的方法制备两个仿生微阵列柔性电极，从两个仿生微阵列柔性电极引出导线，导线与电极使用导电银浆粘合，然后置于90℃烘箱中固化50min；再将上述实施例1中制备得到的离子凝胶介电层置于两个仿生微阵列柔性电极6之间，再用聚酰亚胺胶带密封仿生微阵列柔性电极6四周，即完成柔性压力传感器的组装。Two biomimetic microarray flexible electrodes were prepared according to the method in Example 1 above, and wires were drawn from the two biomimetic microarray flexible electrodes, and the wires and electrodes were bonded with conductive silver paste, and then placed in a 90°C oven to cure for 50 minutes; The ionogel dielectric layer prepared in the above Example 1 is placed between two biomimetic microarray flexible electrodes 6, and then the biomimetic microarray flexible electrodes 6 are sealed around with polyimide tape, that is, the assembly of the flexible pressure sensor is completed. .
上述实施例1中制备得到的仿生微阵列柔性电极的表面形貌如图7所示，从图7中可以看出毫米级别的半圆球阵列上均匀分布大量微米级别大小的锥状结构，这就是经过两次倒模得到的复制有新鲜天鹅绒竹芋叶片表面微结构的PDMS薄膜的表面形貌，每个锥体的直径在15-25μm左右，高度在20-30μm左右。The surface morphology of the biomimetic microarray flexible electrode prepared in the above Example 1 is shown in Figure 7. It can be seen from Figure 7 that a large number of micron-scale cone-shaped structures are uniformly distributed on the millimeter-scale hemispherical array. The surface morphology of the PDMS film replicated with the surface microstructure of fresh velvet arrowroot leaves was obtained after two times of pouring. The diameter of each cone is about 15-25 μm and the height is about 20-30 μm.
测试上述实施例1中组装而成的柔性压力传感器的灵敏度和响应曲线，结果如图8所示。The sensitivity and response curve of the flexible pressure sensor assembled in the above Example 1 were tested, and the results are shown in FIG. 8 .
从图8中可以看出。柔性压力传感器在0-90KPa范围内都具有较高的灵敏度，保证了传感器能在较大测量范围对压力的精确感知，特别地是，在较低的压力区域，灵敏度高达37.5KPa -1，能够感知如脉搏振动等极微弱的压力信号，大大拓宽了柔性传感器的使用范围。 It can be seen from Figure 8. The flexible pressure sensor has high sensitivity in the range of 0-90KPa, which ensures that the sensor can accurately sense pressure in a large measurement range, especially in the lower pressure area, the sensitivity is as high as 37.5KPa -1 , which can Sensing extremely weak pressure signals such as pulse vibration greatly expands the application range of flexible sensors.
测试上述实施例1中组装而成的柔性压力传感器的对人体脉搏进行检测，使用医用胶带将柔性传感器贴敷于志愿者手臂脉搏位置，使用LCR源表对传感器的输出信号进行检测，结果如图9所示。Test the flexible pressure sensor assembled in the above Example 1 to detect the human body pulse, use medical tape to stick the flexible sensor on the pulse position of the volunteer's arm, and use the LCR source meter to detect the output signal of the sensor. The results are shown in the figure 9 shown.
从图9中可以看出，柔性压力传感器能连续地采集到人体脉搏波波形，每个波形中的主波(P波)、潮波(T波)以及重搏波(D波)能够清晰识别，从中可以提取出重要的生理信息用于评估人体的健康状态。As can be seen from Figure 9, the flexible pressure sensor can continuously collect the human pulse waveform, and the main wave (P wave), tidal wave (T wave) and dichotomous wave (D wave) in each waveform can be clearly identified , from which important physiological information can be extracted for evaluating the health status of the human body.
测试上述实施例1中组装而成的柔性压力传感器的对人体足底压力进行检测，使用医用胶带将柔性传感器贴敷于志愿者脚跟位置，使用LCR源表对人体在行走过程中输出信号进行检测，结果如图10所示。The flexible pressure sensor assembled in the above Example 1 was tested to detect the pressure on the sole of the human body. The flexible sensor was applied to the heel of the volunteer with medical tape, and the LCR source meter was used to detect the output signal of the human body during walking. , the results are shown in Figure 10.
从图10中可以看出，当志愿者脚跟接触地面时，传感器信号迅速增加，当志愿者脚跟离开地面时，信号恢复到初始水平，可以通过对压力大小和步频等信息分析志愿者的活动状态。As can be seen from Figure 10, when the volunteer's heel touches the ground, the sensor signal increases rapidly, and when the volunteer's heel leaves the ground, the signal returns to the initial level, and the volunteer's activities can be analyzed by information such as pressure and cadence. state.
以上述仅为本发明的较佳实施方式而已，并不用以限制本发明，凡在本发明的精神和原则之内，所作的任何修改、等同替换、改进等，均应包含在本发明的保护范围之内。The above is only a preferred embodiment of the present invention, and is not intended to limit the present invention. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention should be included in the protection of the present invention. within the range.

Claims (10)

  1. 一种仿生微阵列柔性电极的制备方法，其特征在于，包括以下步骤：A preparation method of a bionic microarray flexible electrode, characterized in that it comprises the following steps:
    提供一具有叶面纹理的植物叶片；providing a plant leaf with foliar texture;
    将PDMS预聚物与固化剂混合后得到PDMS混合物，备用；After the PDMS prepolymer is mixed with the curing agent, the PDMS mixture is obtained, which is for subsequent use;
    将所述PDMS混合物浇注在所述植物叶片上，使PDMS固化，将固化后的PDMS从所述植物叶片上取出得到表面与植物叶片表面相反的模具；The PDMS mixture is poured on the plant leaves, the PDMS is cured, and the cured PDMS is taken out from the plant leaves to obtain a mold whose surface is opposite to the surface of the plant leaves;
    将所述模具的与植物叶片表面相反的表面贴附在设有多个通孔的模板上，将所述模板置于真空吸附装置内，开启真空吸附，将模具与模板分离；The surface of the mold opposite to the surface of the plant leaf is attached to the template provided with a plurality of through holes, the template is placed in a vacuum adsorption device, the vacuum adsorption is turned on, and the mold is separated from the template;
    配制AgNWs分散液，将所述AgNWs分散液喷涂至经过真空吸附后的模具上，经过退火处理，即得仿生微阵列柔性电极。AgNWs dispersion liquid is prepared, the AgNWs dispersion liquid is sprayed onto the mold after vacuum adsorption, and annealed to obtain a biomimetic microarray flexible electrode.
  2. 如权利要求1所述的仿生微阵列柔性电极的制备方法，其特征在于，将所述模具的与植物叶片表面相反的表面贴附在设有多个通孔的模板上之前还包括：将所述PDMS混合物滴入模具的与植物叶片表面相反的表面，再经过旋涂，固化，再将固化后的PDMS从模具中取下得到表面呈微圆锥体的PDMS薄膜；再将所述PDMS薄膜的呈微圆锥体的表面贴附在设有多个通孔的模板上，再经过真空吸附，分离PDMS薄膜与模板；再将所述AgNWs分散液喷涂至经过真空吸附后的PDMS薄膜上，经过退火处理，即得仿生微阵列柔性电极。The method for preparing a biomimetic microarray flexible electrode according to claim 1, wherein before attaching the surface of the mold opposite to the surface of the plant leaf on the template provided with the plurality of through holes, the method further comprises: attaching the The PDMS mixture is dropped into the surface of the mold opposite to the surface of the plant leaf, and then spin-coated and cured, and then the cured PDMS is removed from the mold to obtain a PDMS film with a micro-cone surface; The surface of the micro-cone is attached to the template with a plurality of through holes, and then the PDMS film and the template are separated by vacuum adsorption; then the AgNWs dispersion is sprayed on the PDMS film after vacuum adsorption, and annealed After treatment, the biomimetic microarray flexible electrode is obtained.
  3. 如权利要求2所述的仿生微阵列柔性电极的制备方法，其特征在于，再将所述AgNWs分散液喷涂至经过真空吸附后的PDMS薄膜上之前还包括：将所述PDMS混合物滴入PDMS薄膜的远离呈微圆锥体一侧的表面，再经过旋涂，并使PDMS固化，再将经过固化的PDMS薄膜与模板分离；再将所述AgNWs分散液喷涂至经过固化的PDMS薄膜上，经过退火处理，即得仿生微阵列柔性电极。The method for preparing a biomimetic microarray flexible electrode according to claim 2, wherein before spraying the AgNWs dispersion on the PDMS film after vacuum adsorption, the method further comprises: dropping the PDMS mixture into the PDMS film The surface away from the micro-cone side is spin-coated, and the PDMS is cured, and then the cured PDMS film is separated from the template; the AgNWs dispersion is sprayed onto the cured PDMS film, and annealed After treatment, the biomimetic microarray flexible electrode is obtained.
  4. 如权利要求2所述的仿生微阵列柔性电极的制备方法，其特征在于，将所述PDMS混合物滴入模具的与植物叶片表面相反的表面之前还包括：将所述模具置于醇溶液中进行钝化。The method for preparing a biomimetic microarray flexible electrode according to claim 2, wherein before dripping the PDMS mixture into the surface of the mold opposite to the surface of the plant leaf, the method further comprises: placing the mold in an alcohol solution to carry out passivated.
  5. 如权利要求2所述的仿生微阵列柔性电极的制备方法，其特征在于，将 所述PDMS混合物滴入模具的与植物叶片表面相反的表面，再经过旋涂，固化，其中，旋涂具体为：以300～500r/min的转速旋涂10～20s；固化具体为：于80～100℃下固化20～40min。The method for preparing a biomimetic microarray flexible electrode according to claim 2, wherein the PDMS mixture is dropped into the surface of the mold opposite to the surface of the plant leaf, and then spin-coated and cured, wherein the spin-coating is specifically: : Spin coating at 300～500r/min for 10～20s; curing is as follows: curing at 80～100℃ for 20～40min.
  6. 如权利要求3所述的仿生微阵列柔性电极的制备方法，其特征在于，将所述PDMS混合物滴入PDMS薄膜的远离呈微圆锥体一侧的表面，再经过旋涂，并使PDMS固化，其中，旋涂具体为：以300～500r/min的转速旋涂8～12s；固化具体为：先于红外线灯下加热固化10～20min，再于80～100℃的烘箱中加热40～60min。The method for preparing a biomimetic microarray flexible electrode according to claim 3, wherein the PDMS mixture is dropped into the surface of the PDMS film away from the side of the microcone, spin-coated, and the PDMS is cured, Among them, spin coating is specifically: spin coating at a speed of 300-500r/min for 8-12s; curing is specifically: first heating and curing under an infrared lamp for 10-20min, and then heating in an oven at 80-100°C for 40-60min.
  7. 如权利要求1所述的仿生微阵列柔性电极的制备方法，其特征在于，所述AgNWs分散液的制备方法为：将AgNWs加入至无水乙醇中，超声分散，即得AgNWs分散液；The preparation method of the biomimetic microarray flexible electrode according to claim 1, wherein the preparation method of the AgNWs dispersion liquid is as follows: adding the AgNWs into anhydrous ethanol and ultrasonically dispersing to obtain the AgNWs dispersion liquid;
    和/或，所述退火处理具体为：于80～100℃的烘箱中退火处理40～60min。And/or, the annealing treatment is specifically: annealing treatment in an oven at 80-100° C. for 40-60 minutes.
  8. 一种仿生微阵列柔性电极，其特征在于，采用如权利要求1～7任一所述的制备方法制备得到。A biomimetic microarray flexible electrode is characterized in that, it is prepared by the preparation method according to any one of claims 1 to 7.
  9. 一种柔性压力传感器，其特征在于，包括：A flexible pressure sensor, comprising:
    一对如权利要求8所述的仿生微阵列柔性电极；A pair of bionic microarray flexible electrodes as claimed in claim 8;
    离子凝胶介电层，位于一对所述的仿生微阵列柔性电极之间。The ion gel dielectric layer is located between a pair of the flexible electrodes of the biomimetic microarray.
  10. 如权利要求9所述的柔性压力传感器，其特征在于，所述离子凝胶介电层的制备方法包括以下步骤：The flexible pressure sensor according to claim 9, wherein the preparation method of the ionogel dielectric layer comprises the following steps:
    将PVDF-HFP加入至丙酮中，搅拌均匀后，再加入离子液体，继续搅拌得到混合溶液；Add PVDF-HFP into acetone, stir evenly, then add ionic liquid and continue stirring to obtain a mixed solution;
    将混合溶液涂覆在基底上，然后退火，经过剥离即得离子凝胶介电层。The mixed solution is coated on the substrate, then annealed, and the ion gel dielectric layer is obtained by peeling off.
PCT/CN2021/083921 2021-03-30 2021-03-30 Bionic microarray flexible electrode and preparation method therefor, and flexible pressure sensor WO2022204932A1 (en)

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