WO2023108318A1 - Self-powered flexible pressure sensor - Google Patents

Self-powered flexible pressure sensor Download PDF

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WO2023108318A1
WO2023108318A1 PCT/CN2021/137349 CN2021137349W WO2023108318A1 WO 2023108318 A1 WO2023108318 A1 WO 2023108318A1 CN 2021137349 W CN2021137349 W CN 2021137349W WO 2023108318 A1 WO2023108318 A1 WO 2023108318A1
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flexible
pressure sensor
power supply
zinc
active power
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PCT/CN2021/137349
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French (fr)
Chinese (zh)
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孙洪岩
常煜
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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/CN2021/137349 priority Critical patent/WO2023108318A1/en
Publication of WO2023108318A1 publication Critical patent/WO2023108318A1/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
    • G01L1/16—Measuring force or stress, in general using properties of piezoelectric devices

Definitions

  • the invention belongs to the technical field of pressure sensing, and in particular relates to an active power supply flexible pressure sensor.
  • the present invention addresses the above problems and provides an active power supply flexible pressure sensor.
  • the principle of the pressure sensor By combining the principle of the pressure sensor with a flexible zinc-air battery, the same structural device can simultaneously meet the power supply and pressure sensing functions.
  • An active power supply flexible pressure sensor is a zinc-air battery with a sandwich structure, including an anode and a cathode arranged oppositely, and an ion gel electrolyte sandwiched between the anode and the cathode;
  • the anode is a flexible zinc-containing electrode
  • the cathode is a flexible air electrode
  • the ion gel electrolyte is a film for piezoresistive sensing formed of an ion gel polymer and a flexible substrate.
  • the ion gel electrolyte is obtained by soaking and drying the flexible substrate in the ion gel polymer.
  • the flexible substrate is fiber paper or fiber fabric.
  • the ionogel polymer comprises the following components in parts by mass:
  • the electrolyte is at least one of ammonium chloride, potassium chloride, lithium trifluoromethanesulfonate, zinc chloride, and salts containing zinc ions.
  • the salts containing zinc ions may be zinc trifluoromethanesulfonate and the like.
  • the ionic liquid is -ethyl-methylimidazole trifluoromethanesulfonate ionic liquid.
  • the cathode includes a first flexible conductive substrate, at least the surface of the first flexible conductive substrate in contact with the ion gel electrolyte is coated with a catalyst.
  • the catalyst contained in the catalyst includes at least one of manganese dioxide, nano-carbon material, silver powder or metal material with catalytic performance.
  • the anode includes a second flexible conductive substrate, at least the surface of the second flexible conductive substrate in contact with the ion gel electrolyte is coated with a zinc powder slurry;
  • the anode is zinc foil.
  • first flexible conductive substrate and/or the second flexible conductive substrate is conductive fiber paper or conductive fiber cloth
  • the present invention combines the zinc-air battery with the principle of pressure sensing, and integrates the two into one.
  • the zinc-air battery has the advantages of rich raw materials, safety and environmental protection, high energy density, light weight, non-toxic, harmless and pollution-free, and recyclable.
  • the present invention fundamentally solves the problem of zinc-air batteries by developing ion gel electrolytes.
  • the zinc-air film is flexible, and the traditional alkaline aqueous electrolyte is replaced by an ionic gel electrolyte.
  • the zinc The anode does not have hydrogen evolution side reactions and corrosion problems, effectively improves the anode utilization rate and energy conversion efficiency, and solves the problem of electrolyte drying up, and obtains a flexible zinc-air battery suitable for pressure sensors;
  • the present invention is obtained by immersing and drying the flexible substrate in the ionogel polymer, that is, combining the ionogel polymer with the flexible substrate to form a film material with piezoresistive sensing characteristic structure as the flexible zinc- Solid electrolyte separator for air batteries. Since the flexible substrate is composed of countless fine fibers interspersed and interlaced, and the side wall is wrapped by ion gel polymer, when pressure is applied to the battery, the internal structure of the flexible substrate and the contact area between the electrode and the electrolyte will be changed, increasing the electrode reaction. Active sites, thereby changing the internal resistance of the battery, eventually leading to a change in the output current, which is used as a sensing signal. At the same time, the generated electricity can also drive the operation of low-power devices to form a self-powered pressure sensor.
  • the present invention combines the zinc-air battery with the principle of pressure sensing to obtain a sandwich structure active power supply flexible pressure sensing device.
  • the device is compatible with the dual functions of power generation and pressure sensing, and realizes the integration of power generation and sensing technology.
  • the structure Simple, thin and convenient, self-sufficient in energy, independent and portable, suitable for wearable flexible pressure sensors.
  • the flexible pressure sensor with active power supply in the present invention has various functions. It can generate electricity by itself to drive small electronic devices, and can also detect human physiological signals, etc., which has a bright application prospect.
  • FIG. 1 is a schematic diagram of the structure and principle of an actively powered flexible pressure sensor provided in Embodiment 1 of the present invention
  • Fig. 2 is an LED control diagram of an actively powered flexible pressure sensor provided in Embodiment 1 of the present invention
  • Fig. 3 is a result diagram of an active power supply flexible pressure sensor used in pulse detection provided by Embodiment 1 of the present invention
  • FIG. 4 is a picture of a buzzer regulated by an actively powered flexible pressure sensor provided in Embodiment 1 of the present invention.
  • the term "and/or” describes the association relationship of associated objects, indicating that there may be three relationships, for example, A and/or B may mean: A exists alone, A and B exist simultaneously, and B exists alone Condition. Among them, A and B can be singular or plural.
  • the character "/" generally indicates that the contextual objects are an "or" relationship.
  • the weight of the relevant components mentioned in the description of the embodiments of the present application can not only refer to the specific content of each component, but also represent the proportional relationship between the weights of the various components.
  • the scaling up or down of the content of the fraction is within the scope disclosed in the description of the embodiments of the present application.
  • the mass in the description of the embodiments of the present application may be ⁇ g, mg, g, kg and other well-known mass units in the chemical industry.
  • the invention provides an active power supply flexible pressure sensor, which is a zinc-air battery with a sandwich structure, including an anode and a cathode disposed opposite to each other, and an ion coagulation interposed between the anode and the cathode. gel electrolyte;
  • the anode is a flexible zinc-containing electrode
  • the cathode is a flexible air electrode
  • the ion gel electrolyte is a film for piezoresistive sensing formed of an ion gel polymer and a flexible substrate.
  • the zinc-air battery is combined with the principle of pressure sensing, and the two are integrated into one.
  • the ion gel electrolyte while fundamentally solving the electrolyte leakage problem of the zinc-air battery, makes the zinc-air film flexible, and replaces the traditional alkaline aqueous electrolyte with the ion gel electrolyte, based on the high Excellent thermal stability and negligible vapor pressure, so that the zinc anode does not have the hydrogen evolution side reaction and corrosion problems, effectively improves the anode utilization and energy conversion efficiency, and solves the problem of electrolyte drying, and obtains a flexible zinc-air suitable for pressure sensors Battery; at the same time, the ionogel polymer is combined with the flexible substrate to form a membrane material with piezoresistive sensing characteristics as the solid electrolyte diaphragm of the flexible zinc-air battery.
  • the flexible substrate is composed of countless fine fibers interspersed and interlaced, and the side wall is wrapped by ion gel polymer, when pressure is applied to the battery, the internal structure of the flexible substrate and the contact area between the electrode and the electrolyte will be changed, increasing the electrode reaction. Active sites, thereby changing the internal resistance of the battery, eventually leading to a change in the output current, which is used as a sensing signal. At the same time, the generated electricity can also drive the operation of low-power devices to form a self-powered pressure sensor.
  • a sandwich structure device is assembled by stacking the anode, cathode, and ion gel electrolyte layer by layer. Under pressure, the contact area between the electrode and the ion gel increases, thereby increasing the interface chemical reaction area.
  • the electrodes are connected to the voltage and current detection system. The pressure will cause the device to generate current and change the internal resistance, which will be reflected in the system test current or resistance value. There is a one-to-one relationship between the pressure and the detection current or internal resistance. Therefore, the pressure can be deduced from the current test current or internal resistance value.
  • This embodiment provides an active power supply flexible pressure sensor, the active power supply flexible pressure sensor is a zinc-air battery with a sandwich structure, including an anode 1 and a cathode 2 that are oppositely arranged, and are sandwiched between the anode 1 and the cathode 2 between the ion gel electrolyte 3;
  • the anode 1 is a flexible zinc-containing electrode
  • the cathode 2 is a flexible air electrode
  • the ion gel electrolyte 3 is a film for piezoresistive sensing formed of an ion gel polymer and a flexible substrate.
  • the anode 1 is obtained by coating the zinc powder slurry 12 on the second flexible conductive substrate 11, that is, the conductive paper side, and drying it;
  • the cathode 2 is obtained by coating the catalyst 22, that is, the silver powder slurry, on the first flexible conductive substrate 21. That is, one side of the conductive paper, which is obtained after drying
  • the ion gel electrolyte 3 is obtained by soaking and drying the flexible base material, that is, fiber paper, in the ion gel polymer.
  • the ion gel polymer is polymerized from the following raw materials in parts by mass: 10 parts of polyvinyl alcohol, 30 parts of ionic liquid, 10 parts of electrolyte and 100 parts of water.
  • the preparation process of ion gel electrolyte 3 is: add 10 parts of polyvinyl alcohol (PVA) into 100 parts of distilled water and dissolve to form a hydrogel solution, and then add 30 parts of 1-ethyl-3-methylimidazole trifluoromethanesulfonate in sequence salt ([EMIm]OTF) ionic liquid and 10 parts of NH 4 Cl, and stirred evenly to form an ionic hydrogel; using fiber paper as a diaphragm, soaked in the condensed ion hydrogel, took it out, and dried it in an oven at 80°C to obtain Ion gel electrolyte3.
  • PVA polyvinyl alcohol
  • EMIm]OTF 1-ethyl-3-methylimidazole trifluoromethanesulfonate in sequence salt
  • anode 1, cathode 2 and ion gel electrolyte 3 are directly stacked and assembled into a sandwich structure to form an actively powered flexible pressure sensor.
  • the performance test of the obtained active power supply flexible pressure sensor is also carried out, specifically: as the power supply performance, the open circuit voltage of the test device using a multimeter is ⁇ 1.0V, and the short circuit current density is about ⁇ 3.0mA/cm 2 , as shown in Figure 1 and As shown in Figure 2, the brightness of the LED can be driven by pressure regulation.
  • the open circuit voltage of the test device using a multimeter is ⁇ 1.0V
  • the short circuit current density is about ⁇ 3.0mA/cm 2
  • the brightness of the LED can be driven by pressure regulation.
  • it is used as a wearable sensing application to detect human pulse with high resolution
  • it is used as a self-generating pressure sensor to drive a buzzer.

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  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Measuring Fluid Pressure (AREA)

Abstract

Disclosed is a self-powered flexible pressure sensor. The self-powered flexible pressure sensor is a zinc-air battery having a sandwich structure, and comprises an anode and a cathode disposed opposite to each other, and an ionic gel electrolyte sandwiched between the anode and the cathode. The anode is a flexible zinc-containing electrode, the cathode is a flexible air electrode, and the ionic gel electrolyte is a film formed from an ionic gel polymer and a flexible base material and used to perform piezoresistive sensing. The present invention combines a zinc-air battery and pressure sensing principles to obtain a self-powered flexible pressure sensing device having a sandwich structure. The device has both power generation and pressure sensing functions, thereby achieving integration of power generation and sensing technologies. The device has a simple structure and a compact form, and is convenient to use, self-powered, independently operable, portable, and suitable to serve as a wearable flexible pressure sensor.

Description

一种主动供电柔性压力传感器An Actively Powered Flexible Pressure Sensor 技术领域technical field
本发明属于压力传感技术领域，具体涉及一种主动供电柔性压力传感器。The invention belongs to the technical field of pressure sensing, and in particular relates to an active power supply flexible pressure sensor.
背景技术Background technique
随着智能终端的快速普及，广泛应用在人力生活中如电子皮肤、可穿戴生理监测治疗装置、柔性导电织物、薄膜晶体管和透明薄膜柔性电路等方面的柔性可穿戴电子引发了国内外的持续研究。传感器作为核心部件之一，直接影响可穿戴设备的功能设计与未来发展。其中，柔性可穿戴电子传感器凭借其轻薄便携、电学性能优异和集成度高等特别备受关注。With the rapid popularization of smart terminals, flexible and wearable electronics widely used in human life such as electronic skin, wearable physiological monitoring and treatment devices, flexible conductive fabrics, thin film transistors, and transparent thin film flexible circuits have triggered continuous research at home and abroad. . As one of the core components, sensors directly affect the functional design and future development of wearable devices. Among them, flexible wearable electronic sensors have attracted special attention due to their thinness, portability, excellent electrical performance, and high integration.
近年来，人们已经在可穿戴可植入传感器领域取得了显著进步，例如利用电子皮肤向大脑传递皮肤触觉信息，监测脉搏心率，语音识别，利用三维微电极实现大脑皮层控制假肢，利用人工耳蜗恢复病人听力等。柔性传感单元与传输模块和自持续电源构成了柔性传感器系统。然而，目前大多数传感器都需要外接电源驱动其运行，而且所用的电源系统多数为刚性电池，在可穿戴形式方面会带来一定的问题，导致动力单元成为柔性传感器实现上述特性的最大限制之一。所以，自供电柔性传感技术成为了当前领域的研究焦点。经文献调研发现，现有自供电传感器主要存在两种形式：一是压电/摩擦电纳米发电机传感器，其将受外力产生的电压/电流直接作为传感信号；二是将传感器与柔性电池集成在一起，通过柔性电池给传感器供电。但是，压电/摩擦点纳米发电传感器由于以交流电输出存在的实际输出功率小，以及将电能储 存在电化学电池中存在的时间依赖性和低功耗问题，使其不能作为唯一的动力源可靠和可持续地工作，也不能解决可穿戴设备需要电池的问题。相比来说，将传感器与柔性电池集成在一起引起了广泛关注，但其仍存在传感器的传感材料与柔性电池的供电材料的功能性相似兼容问题。因此，对于低能耗的柔性传感器来说，柔性可调电源或者在没有外部能源供应的情况下自动工作在传感领域变得至关重要，开发主动供电柔性压力传感器十分必要。In recent years, people have made remarkable progress in the field of wearable and implantable sensors, such as using electronic skin to transmit skin tactile information to the brain, monitoring pulse heart rate, speech recognition, using three-dimensional microelectrodes to realize cerebral cortex-controlled prosthetics, and using cochlear implants to restore Patient hearing etc. The flexible sensing unit, transmission module and self-sustaining power supply constitute a flexible sensor system. However, at present, most sensors require an external power supply to drive their operation, and most of the power supply systems used are rigid batteries, which will bring certain problems in wearable forms, causing the power unit to become one of the biggest limitations for flexible sensors to achieve the above characteristics . Therefore, self-powered flexible sensing technology has become the research focus in the current field. According to literature research, there are two main forms of existing self-powered sensors: one is the piezoelectric/triboelectric nanogenerator sensor, which directly uses the voltage/current generated by the external force as the sensing signal; the other is the combination of the sensor and the flexible battery Integrated together, the sensor is powered by a flexible battery. However, due to the small actual output power of the piezoelectric/friction point nano-power generation sensor in the form of an AC output, and the time-dependence and low power consumption of storing electrical energy in an electrochemical cell, it cannot be used as a reliable power source alone. And to work sustainably, it also doesn't solve the problem of wearables needing batteries. In contrast, the integration of sensors and flexible batteries has attracted widespread attention, but it still has the problem of similar functional compatibility between the sensing material of the sensor and the power supply material of the flexible battery. Therefore, for flexible sensors with low energy consumption, flexible adjustable power supply or automatic operation without external energy supply becomes crucial in the field of sensing, it is necessary to develop actively powered flexible pressure sensors.
发明内容Contents of the invention
有鉴于此，本发明针对上述问题，提供一种主动供电柔性压力传感器，通过将压力传感器原理与柔性锌-空气电池相结合，使同一结构器件同时满足供电和压力传感功能。In view of this, the present invention addresses the above problems and provides an active power supply flexible pressure sensor. By combining the principle of the pressure sensor with a flexible zinc-air battery, the same structural device can simultaneously meet the power supply and pressure sensing functions.
本发明所采用的技术方案是：The technical scheme adopted in the present invention is:
一种主动供电柔性压力传感器，该主动供电柔性压力传感器为三明治结构的锌-空气电池，包括相对设置的阳极和阴极，以及夹设在所述阳极和所述阴极之间的离子凝胶电解质；An active power supply flexible pressure sensor, the active power supply flexible pressure sensor is a zinc-air battery with a sandwich structure, including an anode and a cathode arranged oppositely, and an ion gel electrolyte sandwiched between the anode and the cathode;
所述阳极为柔性含锌电极，所述阴极为柔性空气电极，所述离子凝胶电解质为离子凝胶聚合物和柔性基材形成的用于压阻传感的膜。The anode is a flexible zinc-containing electrode, the cathode is a flexible air electrode, and the ion gel electrolyte is a film for piezoresistive sensing formed of an ion gel polymer and a flexible substrate.
进一步地，所述离子凝胶电解质通过将柔性基材于离子凝胶聚合物中浸泡干燥后得到。Further, the ion gel electrolyte is obtained by soaking and drying the flexible substrate in the ion gel polymer.
进一步地，所述柔性基材为纤维纸或纤维织物。Further, the flexible substrate is fiber paper or fiber fabric.
进一步地，所述离子凝胶聚合物包括如下质量份数的成分聚合而成：Further, the ionogel polymer comprises the following components in parts by mass:
聚乙烯醇7～15份，离子液体5～40份，电解质1～20份，水100份。7-15 parts of polyvinyl alcohol, 5-40 parts of ionic liquid, 1-20 parts of electrolyte, and 100 parts of water.
进一步地，所述电解质为氯化铵、氯化钾、三氟甲磺酸锂、氯化锌、含锌离子的盐类中的至少一种。Further, the electrolyte is at least one of ammonium chloride, potassium chloride, lithium trifluoromethanesulfonate, zinc chloride, and salts containing zinc ions.
其中，含锌离子的盐类可以为三氟甲烷磺酸锌等。Wherein, the salts containing zinc ions may be zinc trifluoromethanesulfonate and the like.
进一步地，所述离子液体为-乙基--甲基咪唑三氟甲磺酸盐离子液体。Further, the ionic liquid is -ethyl-methylimidazole trifluoromethanesulfonate ionic liquid.
进一步地，所述阴极包括第一柔性导电基体，至少在所述第一柔性导电基体的与所述离子凝胶电解质接触的表面上涂设有催化剂。Further, the cathode includes a first flexible conductive substrate, at least the surface of the first flexible conductive substrate in contact with the ion gel electrolyte is coated with a catalyst.
进一步地，所述催化剂所含的催化剂包括二氧化锰、纳米碳材料、银粉或具有催化性能的金属材料中的至少一种。Further, the catalyst contained in the catalyst includes at least one of manganese dioxide, nano-carbon material, silver powder or metal material with catalytic performance.
进一步地，所述阳极包括第二柔性导电基体，至少在所述第二柔性导电基体的与所述离子凝胶电解质接触的表面上涂设有锌粉浆料；Further, the anode includes a second flexible conductive substrate, at least the surface of the second flexible conductive substrate in contact with the ion gel electrolyte is coated with a zinc powder slurry;
或者所述阳极为锌箔。Or the anode is zinc foil.
进一步地，所述第一柔性导电基体和/或所述第二柔性导电基体为导电纤维纸或导电纤维布Further, the first flexible conductive substrate and/or the second flexible conductive substrate is conductive fiber paper or conductive fiber cloth
本发明的有益效果是：The beneficial effects of the present invention are:
1、本发明将锌-空气电池与压力传感原理相结合，将二者融二为一。其中，锌-空气电池具有原材料丰富、安全环保、能量密度高、质量轻、无毒无害无污染、可回收循环等优点，本发明通过开发离子凝胶电解质，在从根本上解决锌-空气电池电解液泄露问题的同时，使锌-空气实现薄膜柔性化，而且通过离子凝胶电解质取代传统碱性水系电解液，基于离子液体具有较高的热稳定性和可以忽略的蒸气压，使锌阳极不存在析氢副反应和腐蚀问题，有效提高阳极利用率和能量转化效率，并解决电解液干涸问题，得到适用于压力传感器的柔性锌-空气电池；1. The present invention combines the zinc-air battery with the principle of pressure sensing, and integrates the two into one. Among them, the zinc-air battery has the advantages of rich raw materials, safety and environmental protection, high energy density, light weight, non-toxic, harmless and pollution-free, and recyclable. The present invention fundamentally solves the problem of zinc-air batteries by developing ion gel electrolytes. In addition to the problem of battery electrolyte leakage, the zinc-air film is flexible, and the traditional alkaline aqueous electrolyte is replaced by an ionic gel electrolyte. Based on the high thermal stability and negligible vapor pressure of the ionic liquid, the zinc The anode does not have hydrogen evolution side reactions and corrosion problems, effectively improves the anode utilization rate and energy conversion efficiency, and solves the problem of electrolyte drying up, and obtains a flexible zinc-air battery suitable for pressure sensors;
2、本发明通过将柔性基材于离子凝胶聚合物中浸泡干燥后得到，即采用离子凝胶聚合物与柔性基材结合形成一个具有压阻传感特性结构的膜材料做为柔性锌-空气电池的固态电解质隔膜。由于柔性基材由无数条细纤维 穿插交错组成，侧壁被离子凝胶聚合物包裹，当对电池施加压力时，将会改变柔性基材的内部结构以及电极与电解质的接触面积，增加电极反应活性位点，从而改变电池的内阻，最终导致输出的电流发生变化，并作为传感信号，同时产生的电量还可以带动低功率器件的运行，形成一个自发电的压力传感器。2. The present invention is obtained by immersing and drying the flexible substrate in the ionogel polymer, that is, combining the ionogel polymer with the flexible substrate to form a film material with piezoresistive sensing characteristic structure as the flexible zinc- Solid electrolyte separator for air batteries. Since the flexible substrate is composed of countless fine fibers interspersed and interlaced, and the side wall is wrapped by ion gel polymer, when pressure is applied to the battery, the internal structure of the flexible substrate and the contact area between the electrode and the electrolyte will be changed, increasing the electrode reaction. Active sites, thereby changing the internal resistance of the battery, eventually leading to a change in the output current, which is used as a sensing signal. At the same time, the generated electricity can also drive the operation of low-power devices to form a self-powered pressure sensor.
3、本发明通过将锌-空气电池与压力传感原理相结合，得到三明治结构主动供电柔性压力传感器件，该器件兼容发电和压力传感双功能，实现了发电和传感技术一体化，结构简单，轻薄便捷化，能量自给自足，独立便携，适用作可穿戴柔性压力传感器。3. The present invention combines the zinc-air battery with the principle of pressure sensing to obtain a sandwich structure active power supply flexible pressure sensing device. The device is compatible with the dual functions of power generation and pressure sensing, and realizes the integration of power generation and sensing technology. The structure Simple, thin and convenient, self-sufficient in energy, independent and portable, suitable for wearable flexible pressure sensors.
4、本发明中主动供电柔性压力传感器功能多样，自身发电可以驱动小型电子设备，也可以检测人体生理信号等，具有美好的应用前景。4. The flexible pressure sensor with active power supply in the present invention has various functions. It can generate electricity by itself to drive small electronic devices, and can also detect human physiological signals, etc., which has a bright application prospect.
附图说明Description of drawings
图1为本发明实施例1提供的一种主动供电柔性压力传感器的结构原理示意图；FIG. 1 is a schematic diagram of the structure and principle of an actively powered flexible pressure sensor provided in Embodiment 1 of the present invention;
图2为本发明实施例1提供的一种主动供电柔性压力传感器调控LED图；Fig. 2 is an LED control diagram of an actively powered flexible pressure sensor provided in Embodiment 1 of the present invention;
图3为本发明实施例1提供的一种主动供电柔性压力传感器用于脉搏检测的结果图；Fig. 3 is a result diagram of an active power supply flexible pressure sensor used in pulse detection provided by Embodiment 1 of the present invention;
图4为本发明实施例1提供的一种主动供电柔性压力传感器调控蜂鸣器图片。FIG. 4 is a picture of a buzzer regulated by an actively powered flexible pressure sensor provided in Embodiment 1 of the present invention.
图中：1、阳极；11、第二柔性导电基体；12、锌粉浆料；2、阴极；21、第一柔性导电基体；22、催化剂；3、离子凝胶电解质。In the figure: 1. anode; 11. second flexible conductive substrate; 12. zinc powder slurry; 2. cathode; 21. first flexible conductive substrate; 22. catalyst; 3. ion gel electrolyte.
具体实施方式Detailed ways
为了使本发明的目的、技术方案及优点更加清楚明白，以下结合实施例，对本发明进行进一步详细说明。应当理解，此处所描述的具体实施例仅仅用以解释本发明，并不用于限定本发明，基于本发明中的实施例，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例，都属于本发明保护的范围。In order to make the object, technical solution and advantages of the present invention more clear, the present invention will be further described in detail below in conjunction with the examples. It should be understood that the specific embodiments described here are only used to explain the present invention, and are not used to limit the present invention. Based on the embodiments in the present invention, all other Embodiments all belong to the protection scope of the present invention.
本申请中，术语“和/或”，描述关联对象的关联关系，表示可以存在三种关系，例如，A和/或B，可以表示：单独存在A，同时存在A和B，单独存在B的情况。其中A，B可以是单数或者复数。字符“/”一般表示前后关联对象是一种“或”的关系。In this application, the term "and/or" describes the association relationship of associated objects, indicating that there may be three relationships, for example, A and/or B may mean: A exists alone, A and B exist simultaneously, and B exists alone Condition. Among them, A and B can be singular or plural. The character "/" generally indicates that the contextual objects are an "or" relationship.
本申请中，“至少一个”是指一个或者多个，“多个”是指两个或两个以上。本申请实施例说明书中所提到的相关成分的重量不仅仅可以指代各组分的具体含量，也可以表示各组分间重量的比例关系，因此，只要是按照本申请实施例说明书相关组分的含量按比例放大或缩小均在本申请实施例说明书公开的范围之内。具体地，本申请实施例说明书中的质量可以是μg、mg、g、kg等化工领域公知的质量单位。In this application, "at least one" means one or more, and "multiple" means two or more. The weight of the relevant components mentioned in the description of the embodiments of the present application can not only refer to the specific content of each component, but also represent the proportional relationship between the weights of the various components. The scaling up or down of the content of the fraction is within the scope disclosed in the description of the embodiments of the present application. Specifically, the mass in the description of the embodiments of the present application may be μg, mg, g, kg and other well-known mass units in the chemical industry.
本发明提供一种主动供电柔性压力传感器，该主动供电柔性压力传感器为三明治结构的锌-空气电池，包括相对设置的阳极和阴极，以及夹设在所述阳极和所述阴极之间的离子凝胶电解质；The invention provides an active power supply flexible pressure sensor, which is a zinc-air battery with a sandwich structure, including an anode and a cathode disposed opposite to each other, and an ion coagulation interposed between the anode and the cathode. gel electrolyte;
所述阳极为柔性含锌电极，所述阴极为柔性空气电极，所述离子凝胶电解质为离子凝胶聚合物和柔性基材形成的用于压阻传感的膜。The anode is a flexible zinc-containing electrode, the cathode is a flexible air electrode, and the ion gel electrolyte is a film for piezoresistive sensing formed of an ion gel polymer and a flexible substrate.
这样，将锌-空气电池与压力传感原理相结合，将二者融二为一。离子凝胶电解质，在从根本上解决锌-空气电池电解液泄露问题的同时，使锌-空气实现薄膜柔性化，而且通过离子凝胶电解质取代传统碱性水系电解液，基 于离子液体具有较高的热稳定性和可以忽略的蒸气压，使锌阳极不存在析氢副反应和腐蚀问题，有效提高阳极利用率和能量转化效率，并解决电解液干涸问题，得到适用于压力传感器的柔性锌-空气电池；同时采用离子凝胶聚合物与柔性基材结合形成一个具有压阻传感特性结构的膜材料做为柔性锌-空气电池的固态电解质隔膜。由于柔性基材由无数条细纤维穿插交错组成，侧壁被离子凝胶聚合物包裹，当对电池施加压力时，将会改变柔性基材的内部结构以及电极与电解质的接触面积，增加电极反应活性位点，从而改变电池的内阻，最终导致输出的电流发生变化，并作为传感信号，同时产生的电量还可以带动低功率器件的运行，形成一个自发电的压力传感器。In this way, the zinc-air battery is combined with the principle of pressure sensing, and the two are integrated into one. The ion gel electrolyte, while fundamentally solving the electrolyte leakage problem of the zinc-air battery, makes the zinc-air film flexible, and replaces the traditional alkaline aqueous electrolyte with the ion gel electrolyte, based on the high Excellent thermal stability and negligible vapor pressure, so that the zinc anode does not have the hydrogen evolution side reaction and corrosion problems, effectively improves the anode utilization and energy conversion efficiency, and solves the problem of electrolyte drying, and obtains a flexible zinc-air suitable for pressure sensors Battery; at the same time, the ionogel polymer is combined with the flexible substrate to form a membrane material with piezoresistive sensing characteristics as the solid electrolyte diaphragm of the flexible zinc-air battery. Since the flexible substrate is composed of countless fine fibers interspersed and interlaced, and the side wall is wrapped by ion gel polymer, when pressure is applied to the battery, the internal structure of the flexible substrate and the contact area between the electrode and the electrolyte will be changed, increasing the electrode reaction. Active sites, thereby changing the internal resistance of the battery, eventually leading to a change in the output current, which is used as a sensing signal. At the same time, the generated electricity can also drive the operation of low-power devices to form a self-powered pressure sensor.
具体为，将阳极、阴极、离子凝胶电解质通过层层叠加的方法组装三明治结构器件，在压力作用下，电极与离子凝胶之间的接触面积增加，从而增加了界面化学反应面积。电极连接到电压、电流检测系统，压力导致器件发电电流、内阻大小的改变，将会反映到系统测试电流或电阻值，而压力大小与检测电流或内阻的值是一一对应的关系，因此可由当前测试电流或内阻值反推出压力大小。Specifically, a sandwich structure device is assembled by stacking the anode, cathode, and ion gel electrolyte layer by layer. Under pressure, the contact area between the electrode and the ion gel increases, thereby increasing the interface chemical reaction area. The electrodes are connected to the voltage and current detection system. The pressure will cause the device to generate current and change the internal resistance, which will be reflected in the system test current or resistance value. There is a one-to-one relationship between the pressure and the detection current or internal resistance. Therefore, the pressure can be deduced from the current test current or internal resistance value.
以下通过具体实施例来说明上述技术方案。The above technical solutions are described below through specific examples.
实施例1Example 1
本实施例提供了一种主动供电柔性压力传感器，该主动供电柔性压力传感器为三明治结构的锌-空气电池，包括相对设置的阳极1和阴极2，以及夹设在所述阳极1和所述阴极2之间的离子凝胶电解质3；This embodiment provides an active power supply flexible pressure sensor, the active power supply flexible pressure sensor is a zinc-air battery with a sandwich structure, including an anode 1 and a cathode 2 that are oppositely arranged, and are sandwiched between the anode 1 and the cathode 2 between the ion gel electrolyte 3;
所述阳极1柔性含锌电极，所述阴极2为柔性空气电极，所述离子凝胶电解质3为离子凝胶聚合物和柔性基材形成的用于压阻传感的膜。The anode 1 is a flexible zinc-containing electrode, the cathode 2 is a flexible air electrode, and the ion gel electrolyte 3 is a film for piezoresistive sensing formed of an ion gel polymer and a flexible substrate.
其中，阳极1通过将锌粉浆料12涂布在第二柔性导电基体11即导电纸 一侧，干燥后得到；阴极2通过将催化剂22也就是银粉浆料涂布在第一柔性导电基体21即导电纸一侧，干燥后得到Among them, the anode 1 is obtained by coating the zinc powder slurry 12 on the second flexible conductive substrate 11, that is, the conductive paper side, and drying it; the cathode 2 is obtained by coating the catalyst 22, that is, the silver powder slurry, on the first flexible conductive substrate 21. That is, one side of the conductive paper, which is obtained after drying
离子凝胶电解质3通过将柔性基材即纤维纸于离子凝胶聚合物中浸泡干燥后得到。离子凝胶聚合物包括以下质量份数的原材料聚合而成：聚乙烯醇10份，离子液体30份，电解质10份，水100份。The ion gel electrolyte 3 is obtained by soaking and drying the flexible base material, that is, fiber paper, in the ion gel polymer. The ion gel polymer is polymerized from the following raw materials in parts by mass: 10 parts of polyvinyl alcohol, 30 parts of ionic liquid, 10 parts of electrolyte and 100 parts of water.
离子凝胶电解质3的制备过程为：将10份聚乙烯醇(PVA)加入100份蒸馏水中溶解形成水凝胶溶液，再依次加入30份1-乙基-3-甲基咪唑三氟甲磺酸盐([EMIm]OTF)离子液体和10份NH 4Cl，搅拌均匀形成离子水凝胶；使用纤维纸作为隔膜，放入凝离子水凝胶中浸泡取出，在80℃烘箱中干燥，得到离子凝胶电解质3。 The preparation process of ion gel electrolyte 3 is: add 10 parts of polyvinyl alcohol (PVA) into 100 parts of distilled water and dissolve to form a hydrogel solution, and then add 30 parts of 1-ethyl-3-methylimidazole trifluoromethanesulfonate in sequence salt ([EMIm]OTF) ionic liquid and 10 parts of NH 4 Cl, and stirred evenly to form an ionic hydrogel; using fiber paper as a diaphragm, soaked in the condensed ion hydrogel, took it out, and dried it in an oven at 80°C to obtain Ion gel electrolyte3.
最后，将阳极1、阴极2和离子凝胶电解质3直接叠加组装成三明治结构，形成主动供电式柔性压力传感器。Finally, the anode 1, cathode 2 and ion gel electrolyte 3 are directly stacked and assembled into a sandwich structure to form an actively powered flexible pressure sensor.
本实施例还对得到的主动供电柔性压力传感器进行性能测试，具体为：作为供电性能，使用万用表测试器件的开路电压为～1.0V，短路电流密度约～3.0mA/cm 2，如图1和图2所示，可通过压力调控驱动LED亮度。同时，如图3所示，作为可穿戴传感应用具有较高分辨率检测人体脉搏；如图4所示，作为自发电压力传感器驱动蜂鸣器。 In this embodiment, the performance test of the obtained active power supply flexible pressure sensor is also carried out, specifically: as the power supply performance, the open circuit voltage of the test device using a multimeter is ~1.0V, and the short circuit current density is about ~3.0mA/cm 2 , as shown in Figure 1 and As shown in Figure 2, the brightness of the LED can be driven by pressure regulation. At the same time, as shown in Figure 3, it is used as a wearable sensing application to detect human pulse with high resolution; as shown in Figure 4, it is used as a self-generating pressure sensor to drive a buzzer.
以上所述，仅为本发明较佳的具体实施方式，但本发明的保护范围并不局限于此，任何属于本发明限定范围内不同的比例变化，以及任何熟悉本技术领域的技术人员在本发明揭露的技术范围内，可轻易想到的变化或替换，都应涵盖在本发明的保护范围之内。因此，本发明的保护范围应该以权利要求的保护范围为准。The above is only a preferred embodiment of the present invention, but the scope of protection of the present invention is not limited thereto, any changes in proportions within the scope of the present invention, and any skilled person familiar with the technical field Within the technical scope disclosed by the invention, easily conceivable changes or substitutions shall be covered by the protection scope of the present invention. Therefore, the protection scope of the present invention should be determined by the protection scope of the claims.

Claims (10)

  1. 一种主动供电柔性压力传感器，其特征在于，所述主动供电柔性压力传感器为三明治结构的锌-空气电池，包括相对设置的阳极(1)和阴极(2)，以及夹设在所述阳极(1)和所述阴极(2)之间的离子凝胶电解质(3)；An active power supply flexible pressure sensor is characterized in that, the active power supply flexible pressure sensor is a zinc-air battery with a sandwich structure, including an anode (1) and a cathode (2) that are arranged oppositely, and are sandwiched between the anode ( 1) and the ion gel electrolyte (3) between the cathode (2);
    所述阳极(1)为柔性含锌电极，所述阴极(2)为柔性空气电极，所述离子凝胶电解质(3)为离子凝胶聚合物和柔性基材形成的用于压阻传感的膜。The anode (1) is a flexible zinc-containing electrode, the cathode (2) is a flexible air electrode, and the ion gel electrolyte (3) is formed by an ion gel polymer and a flexible substrate for piezoresistive sensing. membrane.
  2. 根据权利要求1所述的一种主动供电柔性压力传感器，其特征在于，所述离子凝胶电解质(3)通过将柔性基材于离子凝胶聚合物中浸泡干燥后得到。The active power supply flexible pressure sensor according to claim 1, characterized in that the ion gel electrolyte (3) is obtained by soaking and drying the flexible substrate in ion gel polymer.
  3. 根据权利要求2所述的一种主动供电柔性压力传感器，其特征在于，所述柔性基材为纤维纸或纤维织物。The active power supply flexible pressure sensor according to claim 2, wherein the flexible substrate is fiber paper or fiber fabric.
  4. 根据权利要求2或3所述的一种主动供电柔性压力传感器，其特征在于，所述离子凝胶聚合物包括如下质量份数的成分聚合而成：An actively powered flexible pressure sensor according to claim 2 or 3, characterized in that, the ionogel polymer comprises the following components in parts by mass:
    聚乙烯醇7～15份，离子液体5～40份，电解质1～20份，水100份。7-15 parts of polyvinyl alcohol, 5-40 parts of ionic liquid, 1-20 parts of electrolyte, and 100 parts of water.
  5. 根据权利要求4所述的一种主动供电柔性压力传感器，其特征在于，所述电解质为氯化铵、氯化钾、三氟甲磺酸锂、氯化锌、含锌离子的盐类中的至少一种。The active power supply flexible pressure sensor according to claim 4, wherein the electrolyte is ammonium chloride, potassium chloride, lithium trifluoromethanesulfonate, zinc chloride, and salts containing zinc ions. at least one.
  6. 根据权利要求4所述的一种主动供电柔性压力传感器，其特征在于，所述离子液体为1-乙基-3-甲基咪唑三氟甲磺酸盐离子液体。The active power supply flexible pressure sensor according to claim 4, wherein the ionic liquid is 1-ethyl-3-methylimidazolium trifluoromethanesulfonate ionic liquid.
  7. 根据权利要求1所述的一种主动供电柔性压力传感器，其特征在于，所述阴极(2)包括第一柔性导电基体(21)，至少在所述第一柔性导电基体 (21)的与所述离子凝胶电解质(3)接触的表面上涂设有催化剂(22)。The active power supply flexible pressure sensor according to claim 1, characterized in that, the cathode (2) comprises a first flexible conductive base (21), at least between the first flexible conductive base (21) and the A catalyst (22) is coated on the contact surface of the ion gel electrolyte (3).
  8. 根据权利要求7所述的一种主动供电柔性压力传感器，其特征在于，所述催化剂(22)所含的催化剂包括二氧化锰、纳米碳材料、银粉或具有催化性能的金属材料中的至少一种。The active power supply flexible pressure sensor according to claim 7, characterized in that the catalyst contained in the catalyst (22) includes at least one of manganese dioxide, carbon nanomaterials, silver powder or metal materials with catalytic properties kind.
  9. 根据权利要求1所述的一种主动供电柔性压力传感器，其特征在于，所述阳极(1)包括第二柔性导电基体(11)，至少在所述第二柔性导电基体(11)的与所述离子凝胶电解质(3)接触的表面上涂设有锌粉浆料(12)；The active power supply flexible pressure sensor according to claim 1, characterized in that, the anode (1) comprises a second flexible conductive base (11), at least between the second flexible conductive base (11) and the Zinc powder slurry (12) is coated on the contact surface of the ion gel electrolyte (3);
    或者所述阳极(1)为锌箔。Or the anode (1) is zinc foil.
  10. 根据权利要求7或9所述的一种主动供电柔性压力传感器，其特征在于，所述第一柔性导电基体(21)和/或所述第二柔性导电基体(11)为导电纤维纸或导电纤维布。The active power supply flexible pressure sensor according to claim 7 or 9, characterized in that, the first flexible conductive substrate (21) and/or the second flexible conductive substrate (11) is conductive fiber paper or conductive Fiber cloth.
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