Battery type pressure sensor and preparation method and application thereof

Abstract

The invention discloses a battery type pressure sensor as well as a preparation method and application thereof. The battery type pressure sensor comprises a positive electrode, a negative electrode and an elastic ionic gel electrolyte connected between the positive electrode and the negative electrode, the elastic ionic gel electrolyte is prepared from the following raw material components: 1-vinyl-3-butylimidazolium tetrafluoroborate, 1-ethyl-3-methylimidazolium tetrafluoroborate, zinc tetrafluoroborate ionic gel, a cross-linking agent and an initiator; the elastic ionic gel electrolyte is provided with a first surface facing the positive electrode and a second surface facing the negative electrode, the first surface is provided with a first protruding structure connected with the positive electrode, and / or the second surface is provided with a second protruding structure connected with the negative electrode. The battery type pressure sensor can solve the technical problem that a traditional pressure sensing mechanism (piezoresistive type, capacitive type, piezoelectric type, triboelectric type and the like) cannot be compatible with long-time self-energy supply and output of a steady-state response signal in a static mode.

Description

Technical Field

[0001] The present invention belongs to the technical field of pressure sensors, and in particular relates to a battery-type pressure sensor, and a preparation method and application thereof. Background Art

[0002] A pressure sensor is a type of sensor that can detect external pressure signals and output other signals that are easy to read. Common pressure sensors include piezoresistive pressure sensors, capacitive pressure sensors, piezoelectric pressure sensors, and triboelectric pressure sensors. However, most current wearable flexible pressure sensors require complicated wiring and external power supplies, which limits the further development of smart electronic devices.

[0003] To solve the above problems, researchers have mainly improved the structure and materials of pressure sensors (such as triboelectric pressure sensors or piezoelectric pressure sensors), or integrated multifunctional devices to achieve a self-powered working mode of the sensing system. However, triboelectric and piezoelectric pressure sensors are difficult to detect static signals, and the preparation process of multi-device integrated systems is too complicated, costly, and results in large equipment size. Capacitor-type pressure sensors have low power storage capacity, are difficult to power for a long time, and have limited working time.

[0004] The information disclosed in this background technology section is only intended to enhance the understanding of the overall background of the invention and should not be regarded as an acknowledgment or any form of suggestion that the information constitutes the prior art already known to a person skilled in the art. Summary of the invention

[0005] The purpose of the present invention is to provide a battery-type pressure sensor, a preparation method and application thereof, which can solve the technical problem that traditional pressure sensing mechanisms (piezoresistive, capacitive, piezoelectric and triboelectric, etc.) are not compatible with long-term self-power supply and output steady-state response signals in static mode.

[0006] In order to achieve the above-mentioned object, a technical solution provided by a specific embodiment of the present invention is as follows: a battery-type pressure sensor comprises a positive electrode, a negative electrode and an elastic ion gel electrolyte connected between the positive electrode and the negative electrode;

[0007] The elastic ion gel electrolyte comprises the following raw material components: 1-vinyl-3-butyl imidazole tetrafluoroborate, 1-ethyl-3-methyl imidazole tetrafluoroborate and zinc tetrafluoroborate ion gel, a crosslinking agent and an initiator;

[0008] The elastic ion gel electrolyte has a first surface facing the positive electrode and a second surface facing the negative electrode, wherein the first surface is provided with a first protruding structure connected to the positive electrode and / or the second surface is provided with a second protruding structure connected to the negative electrode;

[0009] Wherein, when the distance between the positive electrode and the negative electrode changes, the first protrusion structure undergoes elastic deformation to change the contact area between the first protrusion structure and the positive electrode; and / or, when the distance between the positive electrode and the negative electrode changes, the second protrusion structure undergoes elastic deformation to change the contact area between the second protrusion structure and the negative electrode.

[0010] In one or more embodiments of the present invention, the elastic ion gel electrolyte includes the following raw material components: 1.2 to 4.8 parts of 1-vinyl-3-butyl imidazole tetrafluoroborate, 1.223 to 4.892 parts of 1-ethyl-3-methyl imidazole tetrafluoroborate and 0.57 to 2.27 parts of zinc tetrafluoroborate, 0.0048 to 0.0192 parts of a cross-linking agent and 0.0012 to 0.0048 parts of an initiator.

[0011] In one or more embodiments of the present invention, the cross-sectional area of ​​the cross section of the first protrusion structure gradually increases along the direction from the positive electrode to the negative electrode; and / or,

[0012] Along the direction from the negative electrode to the positive electrode, the cross-sectional area of ​​the cross section of the second protrusion structure gradually increases.

[0013] In one or more embodiments of the present invention, the cross-linking agent is any one of N,N'-methylenebisacrylamide, acrylamide, and acrylic acid; the initiator is any one of dibenzoyl phosphate, dibenzoylphenyl phosphate, chloropyridone, and 2-hydroxy-2-methyl-1-[4-(2-hydroxyethoxy)phenyl]-1-propanone.

[0014] In one or more embodiments of the present invention, the viscosity of the elastic ion gel electrolyte is in the range of 100 to 2000 mPa·s; and the Young's modulus of the elastic ion gel electrolyte is in the range of 5 to 200 kPa.

[0015] In one or more embodiments of the present invention, the material of the positive electrode is a PUF / CNT / MnO2 composite porous material or a hot-pressed PUF / CNT / MnO2 composite porous material, and the material of the negative electrode is a PUF / CNT / Zn composite porous material or a hot-pressed PUF / CNT / Zn composite porous material.

[0016] A specific embodiment of the present invention further provides a method for preparing a battery-type pressure sensor, comprising the following steps:

[0017] Obtaining a positive electrode and a negative electrode;

[0018] 1-vinyl-3-butyl imidazole tetrafluoroborate, 1-ethyl-3-methyl imidazole tetrafluoroborate, zinc tetrafluoroborate ion gel, a crosslinking agent and an initiator are uniformly mixed, placed in a mold, and reacted under ultraviolet light to obtain the elastic ion gel electrolyte as described above;

[0019] The elastic ion gel electrolyte is bonded between the positive electrode and the negative electrode to obtain the battery type pressure sensor.

[0020] In one or more embodiments of the present invention, the step of uniformly mixing 1-vinyl-3-butyl imidazole tetrafluoroborate, 1-ethyl-3-methyl imidazole tetrafluoroborate, zinc tetrafluoroborate ion gel, a crosslinking agent and an initiator comprises:

[0021] Under stirring conditions, 1-vinyl-3-butylimidazolium tetrafluoroborate, 1-ethyl-3-methylimidazolium tetrafluoroborate, zinc tetrafluoroborate ion gel, a crosslinking agent and an initiator are mixed and ultrasonically treated.

[0022] In one or more embodiments of the present invention, the reaction time under ultraviolet light is 1 to 5 minutes.

[0023] A specific embodiment of the present invention further provides an application of the battery-type pressure sensor as described above in a pressure sensor and a flexible electronic skin.

[0024] Compared with the prior art, the battery-type pressure sensor of the present invention effectively improves the battery characteristics and mechanical sensing characteristics of the battery-type pressure sensor by designing the raw material components of the elastic ion gel electrolyte connected between the positive electrode and the negative electrode and the structure of the elastic ion gel electrolyte, so that the battery-type pressure sensor of the present invention can sense the external pressure and convert it into a current output signal without connecting to an external power supply, and reduce the standby power consumption in the absence of external pressure, thereby improving the integration and service life of the pressure sensor. Because of the structural characteristics of the elastic ion gel electrolyte and the low Young's modulus (influenced by the raw material components), it can be beneficial to reduce the lower limit of the device pressure sensing and improve the sensitivity. BRIEF DESCRIPTION OF THE DRAWINGS

[0025] In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings required for use in the embodiments or the description of the prior art will be briefly introduced below. Obviously, the drawings described below are only some embodiments recorded in the present invention. For ordinary technicians in this field, other drawings can be obtained based on these drawings without paying creative work.

[0026] Figure 1 A schematic diagram of the structure of a battery-type pressure sensor in an example of the present invention;

[0027] Figure 2 It is a stress-strain curve diagram of the elastic ion gel electrolyte in Comparative Examples 4 to 7 of the present invention;

[0028] Figure 3 It is a mechanical sensitivity diagram of the sensor in Example 2 of the present invention and Comparative Examples 1 to 3;

[0029] Figure 4 Schematic diagram of the structure of the elastic ion gel electrolyte in Comparative Examples 3 to 7 of the present invention.

[0030] Description of main reference numerals:

[0031] 1. Positive electrode; 2. Negative electrode; 3. Elastic ion gel electrolyte; 31. Main layer; 311. First surface; 312. Second surface; 32. First protruding structure; 33. Second protruding structure. DETAILED DESCRIPTION

[0032] In order to enable those skilled in the art to better understand the technical solutions in the present invention, the technical solutions in the embodiments of the present invention will be clearly and completely described below in conjunction with the drawings in the embodiments of the present invention. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work should fall within the scope of protection of the present invention.

[0033] like Figure 1 As shown, a battery-type pressure sensor in an example of the present invention comprises a positive electrode 1, a negative electrode 2 and an elastic ion gel electrolyte 3 connected between the positive electrode 1 and the negative electrode 2; the elastic ion gel electrolyte 3 comprises the following raw material components: 1-vinyl-3-butyl imidazole tetrafluoroborate, 1-ethyl-3-methyl imidazole tetrafluoroborate and zinc tetrafluoroborate ion gel, a crosslinker and an initiator; the elastic ion gel electrolyte 3 has a first surface 311 facing the positive electrode 1 and a second surface 312 connected to the negative electrode 2, the first surface 311 is provided with a first protrusion structure 32 connected to the positive electrode 1 and / or the second surface 312 is provided with a second protrusion structure 33 connected to the negative electrode 2; wherein, when the distance between the positive electrode 1 and the negative electrode 2 changes, the first protrusion structure 32 undergoes elastic deformation to change the contact area between the first protrusion structure 32 and the positive electrode 1; and / or, when the distance between the positive electrode 1 and the negative electrode 2 changes, the second protrusion structure 33 undergoes elastic deformation to change the contact area between the second protrusion structure 33 and the negative electrode 2.

[0034] It should be noted that in Figure 1In the example shown, the elastic ion gel electrolyte 3 includes a main layer 31, a first surface 311 and a second surface 312 are two opposite surfaces on the main layer 31, the first surface 311 is provided with a first protruding structure 32 bonded to the positive electrode 1, and the second surface 312 is provided with a second protruding structure 33 bonded to the negative electrode 2.

[0035] Under the action of external pressure, when the distance between the positive electrode 1 and the negative electrode 2 becomes smaller, the positive electrode 1 and the negative electrode 2 will squeeze the elastic ion gel electrolyte 3, so that the first protrusion structure 32 and the second protrusion structure 33 will undergo elastic deformation, the contact area between the first protrusion structure 32 and the positive electrode 1 will increase, and the contact area between the second protrusion structure 33 and the negative electrode 2 will increase, so that the open circuit voltage and the external output current signal of the battery-type pressure sensor will change regularly, and the size of the external pressure signal can be reflected according to the above changes. That is, the battery-type pressure sensor of the present invention can realize the sensing of external pressure without an external power supply, and output the current change signal to the outside, which improves the integration of the pressure sensor and simplifies the structure of the pressure sensor.

[0036] When the external pressure disappears, the shape of the elastic ion gel electrolyte 3 can be restored to its original state under the action of its own elastic force, the contact area between the first protrusion structure 32 and the positive electrode 1 and the contact area between the second protrusion structure 33 and the negative electrode 2 will be restored to their original state, and the open circuit voltage and external output current signal of the battery-type pressure sensor will also return to their original values ​​(when there is no external pressure).

[0037] In a specific example, Figure 1 As shown, when the elastic ion gel electrolyte 3 includes both the first protruding structure 32 and the second protruding structure 33, in order to facilitate the preparation of the elastic ion gel electrolyte 3, when preparing the elastic ion gel electrolyte 3, a part of the main layer 31 and the first protruding structure 32 can be integrally formed in a mold, and another part of the main layer 31 and the second protruding structure 33 can be integrally formed in a mold. Since the material of the elastic ion gel electrolyte 3 itself is sticky, the above two parts can be bonded together to obtain the elastic ion gel electrolyte 3.

[0038] In other examples, the elastic ion gel electrolyte 3 may be integrally formed.

[0039] The battery-type pressure sensor of the present invention stores and releases energy through chemical reactions. Compared with a capacitor-type pressure sensor that stores electrical energy through an electric field, the battery-type pressure sensor of the present invention has a higher energy density and is suitable for long-term power supply.

[0040] The battery-type pressure sensor of the present invention not only further improves its strength, flexibility and mechanical stability, but also reduces standby power consumption while ensuring conductivity by compounding and designing the raw material components of the elastic ion gel electrolyte 3.

[0041] When the battery-type pressure sensor of the present invention is in use, an external host computer or electrochemical workstation can be electrically connected to the positive electrode 1 and the negative electrode 2 of the battery-type pressure sensor, so as to receive the current signal transmitted to the outside by the battery-type pressure sensor.

[0042] Specifically, the elastic ion gel electrolyte 3 includes the following raw material components: 1.2 to 4.8 parts of 1-vinyl-3-butyl imidazole tetrafluoroborate, 1.223 to 4.892 parts of 1-ethyl-3-methyl imidazole tetrafluoroborate and 0.57 to 2.27 parts of zinc tetrafluoroborate, 0.0048 to 0.0192 parts of a crosslinking agent, and 0.0012 to 0.0048 parts of an initiator.

[0043] Preferably, the elastic ion gel electrolyte 3 comprises the following raw material components by mass: 3.6 parts of 1-vinyl-3-butyl imidazole tetrafluoroborate, 3.669 parts of 1-ethyl-3-methyl imidazole tetrafluoroborate and 1.6962 parts of zinc tetrafluoroborate, 0.0144 parts of a crosslinking agent and 0.0036 parts of an initiator.

[0044] Preferably, along the direction from the positive electrode 1 to the negative electrode 2 , the cross-sectional area of ​​the cross section of the first protrusion structure 32 gradually increases.

[0045] Preferably, along the direction from the negative electrode 2 to the positive electrode 1 , the cross-sectional area of ​​the cross section of the second protrusion structure 33 gradually increases.

[0046] Preferably, the crosslinking agent is any one of N,N'-methylenebisacrylamide (MBA), acrylamide, and acrylic acid; the initiator is any one of 2-hydroxy-2-methyl-1-[4-(2-hydroxyethoxy)phenyl]-1-propanone (I2959 photoinitiator), dibenzoyl phosphate, dibenzoylphenyl phosphate, and chloropyridone.

[0047] Preferably, the viscosity of the elastic ion gel electrolyte 3 is in the range of 100 to 2000 mPa·s. The viscosity of the elastic ion gel electrolyte 3 should be neither too low nor too high. A too low viscosity is not conducive to bonding with the positive electrode 1 and the negative electrode 2, while a too high viscosity is not conducive to compression sensing.

[0048] Preferably, the Young's modulus of the elastic ion gel electrolyte 3 is 5 to 200 kPa.

[0049] Preferably, the positive electrode 1 and the negative electrode 2 may be porous electrodes. Specifically, the porous electrode may include a composite material consisting of a porous substrate and a conductive carrier supported on the porous substrate. The conductive carrier may include carbon nanotubes, manganese oxide and zinc.

[0050] The working principle of a battery-type pressure sensor is usually to use the mechanical deformation caused by pressure to affect the output voltage or current of the battery, thereby measuring the magnitude of the pressure based on the electrical signal. The role of the elastic ion gel electrolyte 3 is to prevent the electrode from short-circuiting, provide movable free ions, and reduce the standby power consumption of the device under no pressure. When the sensor is subjected to pressure perpendicular to the direction of the electrode, the resistance of the porous electrode and the gel electrolyte decreases under compression, and the contact area between the gel electrolyte and the porous electrode increases. The above changes will increase the output current of the battery-type sensor as the compressive stress increases, and then convert it into a current sensing signal.

[0051] For example, the material of the positive electrode 1 is a PUF / CNT / MnO2 composite porous material or a hot-pressed PUF / CNT / MnO2 composite porous material, and the material of the negative electrode 2 is a PUF / CNT / Zn composite porous material or a hot-pressed PUF / CNT / Zn composite porous material, wherein PUF is a polyurethane foam material, CNT is a carbon nanotube, and MnO2 is a manganese oxide.

[0052] It can be understood that due to the different compression moduli of the porous electrode and the elastic ion gel electrolyte 3, combined with the shape and structure of the elastic ion gel electrolyte 3, it is conducive to forming a gradient structure, reducing the lower detection limit of the pressure sensor, and increasing the upper detection limit of the pressure sensor, thereby expanding the pressure sensing range of the device.

[0053] The theoretical compressive strain ε of a battery-type pressure sensor is in the following range: ε n <ε<ε1;

[0054] Where: ε1 is the compressive strain of the porous electrode or gel electrolyte with the lowest compression modulus under the same pressure, ε n is the compressive strain of the porous electrode or gel electrolyte with the highest compression modulus under the same pressure.

[0055] A specific example of the present invention further provides a method for preparing a battery-type pressure sensor, which can be used to prepare the above-mentioned battery-type pressure sensor. The preparation method comprises the following steps:

[0056] Obtaining a positive electrode and a negative electrode;

[0057] 1-vinyl-3-butyl imidazole tetrafluoroborate, 1-ethyl-3-methyl imidazole tetrafluoroborate, zinc tetrafluoroborate ion gel, a crosslinking agent and an initiator are uniformly mixed, placed in a mold, and reacted under ultraviolet light to obtain the elastic ion gel electrolyte as described above;

[0058] The elastic ion gel electrolyte is bonded between the positive electrode and the negative electrode to obtain a battery-type pressure sensor.

[0059] Specifically, the step of uniformly mixing 1-vinyl-3-butyl imidazole tetrafluoroborate, 1-ethyl-3-methyl imidazole tetrafluoroborate, zinc tetrafluoroborate ion gel, a crosslinking agent and an initiator comprises:

[0060] Under stirring conditions, 1-vinyl-3-butylimidazolium tetrafluoroborate, 1-ethyl-3-methylimidazolium tetrafluoroborate, zinc tetrafluoroborate ion gel, a crosslinking agent and an initiator are mixed and ultrasonically treated.

[0061] Specifically, the reaction time under ultraviolet light is 1 to 5 minutes.

[0062] A specific example of the present invention also provides an application of the battery-type pressure sensor as described above in a pressure sensor and a flexible electronic skin.

[0063] Furthermore, the battery-type pressure sensor of the present invention can be used for electronic skin, human motion signal monitoring, object recognition, human-computer interaction, sports equipment stress detection, automobile tire force detection, mechanical equipment weight detection, etc.

[0064] The battery-type pressure sensor of the present invention, and its preparation method and application will be described in detail below in combination with specific embodiments and comparative examples.

[0065] Example 1

[0066] Preparation of negative electrode:

[0067] Preparation of PUF / CNT / Zn composite porous material: 30 mL CNT solution was added to 30 mL deionized water, and then the PUF was completely immersed in the above mixture and squeezed repeatedly to ensure full immersion, and freeze-dried to obtain the PUF / CNT composite porous material. The PUF / CNT composite porous material was immersed in a Zn powder solution with PVDF and NMP as solvents, and then placed in a vacuum oven at 70 ° C for drying to obtain the PUF / CNT / Zn composite porous material.

[0068] Using a metal plate fixing device with screw locking, the PUF / CNT / Zn composite porous material was uniaxially compressed by 67% in the opposite direction of the stretching direction, and then placed in a vacuum oven at 140°C for hot pressing for 10 hours. After cooling at room temperature, the hot-pressed composite porous material PUF / CNT / Zn-HP was obtained.

[0069] Preparation of positive electrode:

[0070] Preparation of PUF / CNT / MnO2 composite porous material: 30mL CNT solution was added to 30mL deionized water, and then the PUF was completely immersed in the above mixture and squeezed repeatedly to ensure full impregnation, and freeze-dried to obtain the PUF / CNT composite porous material. The PUF / CNT composite porous material was immersed in KMnO4 solution, and then placed in a 150℃ oven for 5h, and then the material was placed in a 70℃ vacuum oven to dry, and the PUF / CNT / MnO2 composite porous material was obtained.

[0071] Using a metal plate fixing device with screw locking, the PUF / CNT / MnO2 composite porous material was uniaxially compressed by 67% in the opposite direction of the stretching direction, and then placed in a vacuum oven at 140°C for hot pressing for 10 hours. After cooling at room temperature, the hot-pressed composite porous material PUF / CNT / MnO2-HP was obtained.

[0072] Example 2

[0073] Preparation of elastic ion gel electrolyte:

[0074] Under continuous magnetic stirring, 3.669 g of 1-ethyl-3-methylimidazolium tetrafluoroborate, 1.6962 g of zinc tetrafluoroborate, 3.6 g of 1-vinyl-3-butylimidazolium tetrafluoroborate, 0.0144 g of MBA and 0.0036 g of I2959 were added in order. After all the above were added, stirring was continued, and then ultrasonication was performed for 30 minutes. The ionic liquid was poured into a specific mold and irradiated under a certain power of ultraviolet light for 1 minute to obtain the following. Figure 1 Elastic ion gel electrolyte in the shape shown.

[0075] Preparation of battery type pressure sensor:

[0076] By utilizing the viscosity of the elastic ion gel electrolyte itself, the PUF / CNT / Zn and PUF / CNT / MnO2-HP in Example 1 are respectively bonded to the upper and lower surfaces of the elastic ion gel electrolyte to form a sandwich structure, thereby obtaining the battery-type pressure sensor of the present invention.

[0077] Example 3

[0078] Preparation of elastic ion gel electrolyte:

[0079] Under continuous magnetic stirring, 1.223 g of 1-ethyl-3-methylimidazolium tetrafluoroborate, 2.27 g of zinc tetrafluoroborate, 1.2 g of 1-vinyl-3-butylimidazolium tetrafluoroborate, 0.0192 g of MBA and 0.0048 g of I2959 were added in order. After all the above were added, stirring was continued, and then ultrasonication was performed for 30 minutes. The ionic liquid was poured into a specific mold and irradiated under a certain power of ultraviolet light for 1 minute to obtain the following Figure 1 Elastic ion gel electrolyte in the shape shown.

[0080] Example 4

[0081] Preparation of elastic ion gel electrolyte:

[0082] Under continuous magnetic stirring, 4.892 g of 1-ethyl-3-methylimidazolium tetrafluoroborate, 0.57 g of zinc tetrafluoroborate, 4.8 g of 1-vinyl-3-butylimidazolium tetrafluoroborate, 0.0096 g of MBA and 0.0048 g of I2959 were added in order. After all the above were added, stirring was continued, and then ultrasonication was performed for 30 minutes. The ionic liquid was poured into a specific mold and irradiated under a certain power of ultraviolet light for 1 minute to obtain Figure 1 Elastic ion gel electrolyte in the shape shown.

[0083] Comparative Example 1

[0084] Preparation of elastic ion gel electrolyte:

[0085] Under continuous magnetic stirring, 3.669 g of 1-ethyl-3-methylimidazolium tetrafluoroborate, 1.6962 g of zinc tetrafluoroborate, 3.6 g of 1-vinyl-3-butylimidazolium tetrafluoroborate, 0.0144 g of MBA and 0.0036 g of I2959 were added in order. After all the above were added, stirring was continued, and then ultrasonication was performed for 30 minutes. The ionic liquid was poured into a specific mold and irradiated under a certain power of ultraviolet light for 1 minute to obtain Figure 1 Elastic ion gel electrolyte in the shape shown.

[0086] Preparation of battery type pressure sensor electrodes:

[0087] By utilizing the viscosity of the elastic ion gel electrolyte itself, the PUF / CNT / Zn and PUF / CNT / MnO2 in Example 1 are respectively bonded to the upper and lower surfaces of the elastic ion gel electrolyte to form a sandwich structure, thereby obtaining a battery-type pressure sensor.

[0088] Comparative Example 2

[0089] Preparation of elastic ion gel electrolyte:

[0090] Under continuous magnetic stirring, 3.669 g of 1-ethyl-3-methylimidazolium tetrafluoroborate, 1.6962 g of zinc tetrafluoroborate, 3.6 g of 1-vinyl-3-butylimidazolium tetrafluoroborate, 0.0144 g of MBA and 0.0036 g of I2959 were added in order. After all the above were added, stirring was continued, and then ultrasonication was performed for 30 minutes. The ionic liquid was poured into a specific mold and irradiated under a certain power of ultraviolet light for 1 minute to obtain Figure 1 Elastic ion gel electrolyte in the shape shown.

[0091] Preparation of battery type pressure sensor electrodes:

[0092] By utilizing the viscosity of the elastic ion gel electrolyte itself, the PUF / CNT / Zn-HP and PUF / CNT / MnO2-HP in Example 1 are respectively bonded to the upper and lower surfaces of the elastic ion gel electrolyte to form a sandwich structure, thereby obtaining a battery-type pressure sensor.

[0093] Comparative Example 3

[0094] Preparation of elastic ion gel electrolyte:

[0095] Under continuous magnetic stirring, 3.669 g of 1-ethyl-3-methylimidazolium tetrafluoroborate, 1.6962 g of zinc tetrafluoroborate, 3.6 g of 1-vinyl-3-butylimidazolium tetrafluoroborate, 0.0144 g of MBA and 0.0036 g of I2959 were added in order. After all the above were added, stirring was continued, and then ultrasonication was performed for 30 minutes. The ionic liquid was poured into a planar mold and irradiated under a certain power of ultraviolet light for 1 minute to obtain a planar elastic ion gel electrolyte (such as Figure 4 shown).

[0096] Preparation of battery type pressure sensor electrodes:

[0097] By utilizing the viscosity of the elastic ion gel electrolyte itself, the PUF / CNT / Zn and PUF / CNT / MnO2-HP in Example 1 are respectively bonded to the upper and lower surfaces of the elastic ion gel electrolyte to form a sandwich structure, thereby obtaining a battery-type pressure sensor.

[0098] Comparative Example 4

[0099] Preparation of elastic ion gel electrolyte:

[0100] The same as Example 2, the only difference is that the amount of 1-vinyl-3-butyl imidazole tetrafluoroborate is 1.2 g, and the shape of the elastic ion gel electrolyte is as follows Figure 4 shown.

[0101] Comparative Example 5

[0102] Preparation of elastic ion gel electrolyte:

[0103] The same as Example 2, the only difference is that 1-vinyl-3-butyl imidazole tetrafluoroborate is 2.4 g, and the shape of the elastic ion gel electrolyte is as follows Figure 4 shown.

[0104] Comparative Example 6

[0105] Preparation of elastic ion gel electrolyte:

[0106] The same as Example 2, the only difference is that 1-vinyl-3-butyl imidazole tetrafluoroborate is 3.6 g, and the shape of the elastic ion gel electrolyte is as follows Figure 4 shown.

[0107] Comparative Example 7

[0108] Preparation of elastic ion gel electrolyte:

[0109] The same as Example 2, the only difference is that 1-vinyl-3-butyl imidazole tetrafluoroborate is 4.8g, and the shape of the elastic ion gel electrolyte is as follows Figure 4 shown.

[0110] The elastic ion gel electrolytes in Comparative Examples 4 to 7 were subjected to mechanical stress and strain tests using a mechanical testing machine, and the results were as follows: Figure 2 The test results are shown, where the black line corresponds to ratio 4, the red line corresponds to ratio 5, the blue line corresponds to ratio 6, and the green line corresponds to ratio 7.

[0111] Through the mechanical stress-strain test of the elastic ion gel electrolyte, it can be found that when the other components remain unchanged, when the 1-vinyl-3-butylimidazolium tetrafluoroborate is 3.6g, the corresponding elastic ion gel electrolyte has the best mechanical stress-strain performance.

[0112] That is, after changing the shape of the elastic ion gel electrolyte, with other components unchanged, 1-vinyl-3-butyl imidazole tetrafluoroborate is 3.6g of the elastic ion gel electrolyte (changed to Figure 1 The corresponding mechanical stress-strain properties should also be the best.

[0113] The sensors in Example 2 and Comparative Examples 1 to 3 were subjected to mechanical sensitivity tests using a mechanical testing machine, and the results were as follows: Figure 3 The test results shown, wherein the red line corresponds to Example 2, the green line corresponds to Example 1, the blue line corresponds to Example 2, and the black line corresponds to Example 3.

[0114] Through the combination of device structures by controlling whether to perform hot pressing and the shape of the gel in the embodiments and comparative examples and the corresponding test results, it was found that the device sensitivity of comparative example 2 was the lowest but the upper limit of mechanical sensing was the largest; the device sensitivity of comparative example 1 was relatively high but the mechanical sensing range was the smallest; compared with comparative example 3, the combination sensitivity of the dome-shaped ion gel in embodiment 2 was significantly higher than that of the planar ion gel. Therefore, the battery-type pressure sensor of the present invention has the advantages of a wider sensing range and high sensitivity.

[0115] In addition, the performance of the battery type pressure sensor in Examples 3 to 4 is close to the performance of the battery type pressure sensor in Example 2.

[0116] It will be apparent to those skilled in the art that the invention is not limited to the details of the exemplary embodiments described above and that the invention can be implemented in other specific forms without departing from the spirit or essential features of the invention. Therefore, the embodiments should be considered exemplary and non-limiting in all respects, and the scope of the invention is defined by the appended claims rather than the foregoing description, and it is intended that all variations falling within the meaning and scope of the equivalent elements of the claims be included in the invention. Any reference numeral in a claim should not be considered as limiting the claim to which it relates.

[0117] In addition, it should be understood that although the present specification is described according to implementation modes, not every implementation mode contains only one independent technical solution. This description of the specification is only for the sake of clarity. Those skilled in the art should regard the specification as a whole. The technical solutions in each embodiment may also be appropriately combined to form other implementation modes that can be understood by those skilled in the art.

Claims

1. A battery-type pressure sensor, characterized in that: It includes a positive electrode, a negative electrode and an elastic ion gel electrolyte connected between the positive electrode and the negative electrode; The elastic ion gel electrolyte comprises the following raw material components: 1-vinyl-3-butyl imidazole tetrafluoroborate, 1-ethyl-3-methyl imidazole tetrafluoroborate and zinc tetrafluoroborate ion gel, a crosslinking agent and an initiator; The elastic ion gel electrolyte has a first surface facing the positive electrode and a second surface facing the negative electrode, wherein the first surface is provided with a first protruding structure connected to the positive electrode and / or the second surface is provided with a second protruding structure connected to the negative electrode; Wherein, when the distance between the positive electrode and the negative electrode changes, the first protrusion structure undergoes elastic deformation to change the contact area between the first protrusion structure and the positive electrode; and / or, when the distance between the positive electrode and the negative electrode changes, the second protrusion structure undergoes elastic deformation to change the contact area between the second protrusion structure and the negative electrode.

2. The battery type pressure sensor according to claim 1, characterized in that: The elastic ion gel electrolyte comprises the following raw material components by weight: 1.2 to 4.8 parts of 1-vinyl-3-butyl imidazole tetrafluoroborate, 1.223 to 4.892 parts of 1-ethyl-3-methyl imidazole tetrafluoroborate and 0.57 to 2.27 parts of zinc tetrafluoroborate, 0.0048 to 0.0192 parts of a crosslinking agent and 0.0012 to 0.0048 parts of an initiator.

3. The battery type pressure sensor according to claim 1, characterized in that: Along the direction from the positive electrode to the negative electrode, the cross-sectional area of ​​the cross section of the first protrusion structure gradually increases; and / or, Along the direction from the negative electrode to the positive electrode, the cross-sectional area of ​​the cross section of the second protrusion structure gradually increases.

4. The battery type pressure sensor according to claim 1, characterized in that: The crosslinking agent is any one of N,N'-methylenebisacrylamide, acrylamide, and acrylic acid; the initiator is any one of dibenzoyl phosphate, dibenzoylphenyl phosphate, chloropyridone, and 2-hydroxy-2-methyl-1-[4-(2-hydroxyethoxy)phenyl]-1-propanone.

5. The battery type pressure sensor according to claim 1, characterized in that: The viscosity of the elastic ion gel electrolyte is in the range of 100 to 2000 mPa·s; the Young's modulus of the elastic ion gel electrolyte is in the range of 5 to 200 kPa.

6. The battery type pressure sensor according to claim 1, characterized in that: The material of the positive electrode is a PUF / CNT / MnO2 composite porous material or a hot-pressed PUF / CNT / MnO2 composite porous material, and the material of the negative electrode is a PUF / CNT / Zn composite porous material or a hot-pressed PUF / CNT / Zn composite porous material.

7. A method for preparing a battery-type pressure sensor, characterized in that: The following steps are involved: Obtaining a positive electrode and a negative electrode; 1-vinyl-3-butyl imidazole tetrafluoroborate, 1-ethyl-3-methyl imidazole tetrafluoroborate, zinc tetrafluoroborate ion gel, a crosslinking agent and an initiator are uniformly mixed, placed in a mold, and reacted under ultraviolet light to obtain the elastic ion gel electrolyte according to any one of claims 1 to 6; The elastic ion gel electrolyte is bonded between the positive electrode and the negative electrode to obtain the battery type pressure sensor.

8. The method for preparing a battery-type pressure sensor according to claim 7, characterized in that: The step of uniformly mixing 1-vinyl-3-butyl imidazole tetrafluoroborate, 1-ethyl-3-methyl imidazole tetrafluoroborate, zinc tetrafluoroborate ion gel, a crosslinking agent and an initiator comprises: Under stirring conditions, 1-vinyl-3-butylimidazolium tetrafluoroborate, 1-ethyl-3-methylimidazolium tetrafluoroborate, zinc tetrafluoroborate ion gel, a crosslinking agent and an initiator are mixed and ultrasonically treated.

9. The method for preparing a battery-type pressure sensor according to claim 7, characterized in that: The reaction time under ultraviolet light is 1 to 5 minutes.

10. Use of the battery-type pressure sensor according to any one of claims 1 to 6 in a pressure sensor and a flexible electronic skin.

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