CN110736420B - A kind of preparation method of portable self-powered hydrogel strain sensor - Google Patents
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Abstract
一种便携式自供能水凝胶应变传感器的制备方法，主要是通过选用具有优异拉伸性能的柔性水凝胶作为电解质，在其两端分别组装金属锌片作为负极，金属铜片作为正极，构筑一个柔性水凝胶电池。然后在电池的正负极之间连接一个定值电阻作为信号输出端，构筑成应变传感器。借助电池正负两极间化学能向电能的转化，在定值电阻的两端可以检测到电压信号，即传感器的检测信号。当作为主要基体的水凝胶材料受到外力作用而发生形变时，这一变化会引起其内在电阻值的改变，从而导致输出端电压的改变。因此，可通过检测电压信号达到对外力变化的监测。同时，由于水凝胶电池的自供能效应，该应变传感器无需外接电源，可以微型化制备，具有很好的便携性。
A preparation method of a portable self-powered hydrogel strain sensor is mainly constructed by selecting a flexible hydrogel with excellent tensile properties as an electrolyte, assembling metal zinc sheets as negative electrodes and metal copper sheets as positive electrodes at both ends of the flexible hydrogels respectively. A flexible hydrogel battery. Then connect a fixed-value resistor between the positive and negative electrodes of the battery as a signal output terminal to construct a strain sensor. With the help of the conversion of chemical energy between the positive and negative poles of the battery to electrical energy, a voltage signal can be detected at both ends of the fixed-value resistor, that is, the detection signal of the sensor. When the hydrogel material as the main matrix is deformed by external force, this change will cause the change of its intrinsic resistance value, which will lead to the change of the output voltage. Therefore, the monitoring of the change of the external force can be achieved by detecting the voltage signal. At the same time, due to the self-powered effect of the hydrogel battery, the strain sensor does not require an external power supply, can be fabricated in miniaturization, and has good portability.
Description
技术领域technical field
本发明涉及应变传感器的制备方法，属于传感器领域。特别涉及一种无需外加电源，便携，基于原电池原理的自供能应变传感器的设计与制备方法。The invention relates to a preparation method of a strain sensor, and belongs to the field of sensors. In particular, it relates to a design and preparation method of a self-powered strain sensor based on the principle of primary battery, without external power supply, being portable.
背景技术Background technique
基于水凝胶的应变传感器可将微小的机械刺激(如压力和拉力)导致的水凝胶形状变化转换为可测量的电学信号，同时，由于水凝胶具有良好的拉伸性，柔韧性，生物亲和性以及自修复性等特点，使得基于水凝胶的应变传感器在制备与人类健康相关领域的电子设备，例如，脉搏检测器，软体机器人，超级电容器和人造皮肤等方面具有很好的潜在应用前景而受到越来越多的关注。到目前为止，已报道的基于水凝胶的应变传感器按检测信号的不同主要可分为两类：一种是检测因外力刺激导致水凝胶发生形状变化时所引起的电阻值变化，也称为电阻传感器；另一种是检测外力存在时因水凝胶形状改变而产生的电容变化，也称为电容传感器。但这些已报道的传感器绝大多数需要外部电源的驱动以实现其功能，不利于电子设备的微型化，降低了其便携性。然而，目前关于构筑无需外接电源，具有自供能功能的水凝胶应变传感器还鲜有报道。Hydrogel-based strain sensors can convert hydrogel shape changes caused by tiny mechanical stimuli (such as pressure and tension) into measurable electrical signals. At the same time, due to the good stretchability and flexibility of hydrogels, Biocompatibility and self-healing properties make hydrogel-based strain sensors useful in the fabrication of electronic devices related to human health, such as pulse detectors, soft robots, supercapacitors, and artificial skin. The potential application prospects have attracted more and more attention. So far, the reported hydrogel-based strain sensors can be divided into two categories according to the difference of detection signals: one is to detect the resistance value change caused by the shape change of the hydrogel caused by external force stimulation, also called It is a resistive sensor; the other is to detect the capacitance change caused by the change of the shape of the hydrogel in the presence of external force, also known as a capacitive sensor. However, most of these reported sensors require external power to realize their functions, which is not conducive to the miniaturization of electronic devices and reduces their portability. However, there are few reports on the construction of self-powered hydrogel strain sensors without external power supply.
发明内容SUMMARY OF THE INVENTION
本发明目的在于针对目前已报导的水凝胶传感器，绝大多数需要外接电源来驱动，不利于设备便携化的缺点，提供一种基于原电池原理的便携式自供能水凝胶应变传感器的制备方法。The purpose of the present invention is to provide a preparation method of a portable self-powered hydrogel strain sensor based on the principle of primary battery, in view of the shortcomings of the currently reported hydrogel sensors, most of which require an external power source to drive, which is not conducive to the portability of the equipment .
本发明的技术方案是利用具有一定机械性能的水凝胶作为电解质，选择活泼金属作为负极材料，依据原电池原理，构建水凝胶电池。随后通过增加一个定值电阻构成电路回路而实现一个自供能水凝胶应变传感器制备。此传感器的信号输出端为定值电阻的两端，输出信号为电压，表达式为
本发明的具体步骤如下：The concrete steps of the present invention are as follows:
(1)水凝胶的制备(1) Preparation of hydrogel
将明胶和单宁酸以质量比为0.7:1的比例溶于80℃的去离子水中，搅拌两小时，将所得沉淀物冷却后塑型即可使用；Dissolve gelatin and tannic acid in deionized water at 80°C in a mass ratio of 0.7:1, stir for two hours, cool the obtained precipitate and then shape it for use;
(2)原电池的构建(2) Construction of primary battery
将作为原电池负极材料的锌片和作为原电池正极材料的铜片贴附于水凝胶的两侧，以水凝胶作为电解质，构成原电池；The zinc sheet as the negative electrode material of the primary battery and the copper sheet as the positive electrode material of the primary battery are attached to both sides of the hydrogel, and the hydrogel is used as the electrolyte to form a primary battery;
(3)自供能水凝胶应变传感器的制备；(3) Preparation of self-powered hydrogel strain sensor;
选用具有一定阻值的定值电阻连接于原电池的正负电极两端，构成一个电路回路，完成自供能水凝胶应变传感器的构建。以定值电阻的两端为信号输出端，输出的信号为电压信号，此即为所制备传感器的检测信号。A fixed-value resistor with a certain resistance value is selected and connected to both ends of the positive and negative electrodes of the primary battery to form a circuit loop to complete the construction of a self-powered hydrogel strain sensor. The two ends of the fixed-value resistor are used as signal output terminals, and the output signal is a voltage signal, which is the detection signal of the prepared sensor.
进一步地，步骤(1)所述的明胶与单宁酸的质量比可以在0.1：1至1:1范围内调节。Further, the mass ratio of gelatin and tannic acid described in step (1) can be adjusted within the range of 0.1:1 to 1:1.
进一步地，在步骤(1)所述的明胶单宁酸复合水凝胶能替换为其它可用做电池电解质且具有一定机械性能的水凝胶。Further, the gelatin-tannin composite hydrogel described in step (1) can be replaced by other hydrogels that can be used as battery electrolytes and have certain mechanical properties.
进一步地，在步骤(2)所述的金属锌片能替换为其他可用于原电池负极的活泼金属材料。Further, the metal zinc sheet described in step (2) can be replaced with other active metal materials that can be used for the negative electrode of the primary battery.
进一步地，在步骤(2)所述的正极材料能替换为其它能与所选用的负极材料构成原电池反应的材料，也可以是空气电极。Further, the positive electrode material described in step (2) can be replaced with a material that can react with the selected negative electrode material to form a galvanic cell reaction, or it can be an air electrode.
进一步地，步骤(2)所述的金属电极除了可直接使用金属片外，也可以通过真空蒸镀等方式在水凝胶两端镀上金属电极膜层，电极在水凝胶上的组装方式不限。Further, in addition to using metal sheets directly, the metal electrodes in step (2) can also be plated with metal electrode film layers on both ends of the hydrogel by vacuum evaporation and other methods. The assembly method of the electrodes on the hydrogel Unlimited.
进一步地，步骤(3)所述的定值电阻可以为任意值，当其阻值与水凝胶的初始电阻一样大时，该自供能应变传感器在初始状态的灵敏度达到最大。Further, the fixed-value resistance in step (3) can be any value, and when the resistance value is as large as the initial resistance of the hydrogel, the sensitivity of the self-powered strain sensor in the initial state reaches the maximum.
本发明所述方法特征之一是选用水凝胶作为原电池的电解质，水凝胶的三维立体网络结构和高含水量使其利于离子传输，具有一定的导电性，可以作为电解质材料。此外，水凝胶的电阻会随其应变而发生改变。特征之二是基于原电池原理，构建自供能水凝胶应变传感器，将原电池反应的化学能转化为电能，无需额外的外部电源支持。当水凝胶受到外力刺激而发生应变时，其电阻的改变引起传感器输出电压信号发生变化，达到检测的目的。One of the characteristics of the method of the present invention is that hydrogel is selected as the electrolyte of the primary battery. The three-dimensional network structure and high water content of the hydrogel make it favorable for ion transport, have certain conductivity, and can be used as an electrolyte material. In addition, the electrical resistance of the hydrogel changes as it is strained. The second feature is to build a self-powered hydrogel strain sensor based on the principle of a galvanic cell, which converts the chemical energy of the galvanic cell reaction into electrical energy without additional external power support. When the hydrogel is stimulated and strained by external force, the change of its resistance causes the output voltage signal of the sensor to change, so as to achieve the purpose of detection.
与已报道的水凝胶应变传感器的方法相比，本发明制备的应变传感器由于自供能，无需外接电源，而易于微型化设计，增加了传感器的便携性，并且制备方法非常简便易行。Compared with the reported method of hydrogel strain sensor, the strain sensor prepared by the present invention is easy to be miniaturized and designed because of self-supply and no external power supply, which increases the portability of the sensor, and the preparation method is very simple and easy.
附图说明Description of drawings
图1为便携式自供能水凝胶应变传感器的结构示意图。Figure 1 is a schematic structural diagram of a portable self-powered hydrogel strain sensor.
具体实施方式Detailed ways
实施例1Example 1
(1)水凝胶的制备(1) Preparation of hydrogel
将明胶和单宁酸以质量比为0.7:1的比例溶于80℃的去离子水中，搅拌两小时，将所得沉淀物冷却塑型即可得到目标水凝胶；Dissolve gelatin and tannic acid in deionized water at 80°C in a mass ratio of 0.7:1, stir for two hours, and cool and shape the obtained precipitate to obtain the target hydrogel;
(2)原电池的构建(2) Construction of primary battery
将作为原电池负极材料的锌片和作为原电池正极材料的铜片贴附于水凝胶两侧的两端，构成原电池；A galvanic battery is formed by attaching the zinc sheet as the negative electrode material of the primary battery and the copper sheet as the positive electrode material of the primary battery on both ends of the hydrogel;
(3)自供能应变传感器的制备；(3) Preparation of self-powered strain sensor;
将100Ω定值电阻连接于原电池的正负极，定值电阻的两端为信号输出点，输出的信号为电压信号，即可实现自供能应变传感器的制备。The 100Ω fixed-value resistor is connected to the positive and negative electrodes of the primary battery, the two ends of the fixed-value resistor are signal output points, and the output signal is a voltage signal, and the preparation of the self-powered strain sensor can be realized.
实施例2Example 2
(1)水凝胶的制备(1) Preparation of hydrogel
将明胶和单宁酸以质量比为0.9:1的比例溶于80℃的去离子水中，搅拌两小时，将所得沉淀物冷却塑型即可得到目标水凝胶；Dissolve gelatin and tannic acid in deionized water at 80° C. in a mass ratio of 0.9:1, stir for two hours, and cool and shape the obtained precipitate to obtain the target hydrogel;
(2)原电池的构建(2) Construction of primary battery
将作为原电池负极材料的锌片和作为原电池正极材料的铜片贴附于水凝胶两侧的两端，构成原电池；A galvanic battery is formed by attaching the zinc sheet as the negative electrode material of the primary battery and the copper sheet as the positive electrode material of the primary battery on both ends of the hydrogel;
(3)自供能应变传感器的制备；(3) Preparation of self-powered strain sensor;
将1kΩ定值电阻连接于原电池的正负极，定值电阻的两端为信号输出点，输出的信号为电压信号，即可实现自供能应变传感器的制备。The 1kΩ fixed-value resistor is connected to the positive and negative electrodes of the primary battery, the two ends of the fixed-value resistor are signal output points, and the output signal is a voltage signal, and the preparation of the self-powered strain sensor can be realized.
实施例3Example 3
(1)水凝胶的制备(1) Preparation of hydrogel
将明胶和单宁酸以质量比为0.7:1的比例溶于80℃的去离子水中，搅拌两小时，将所得沉淀物冷却塑型即可得到目标水凝胶；Dissolve gelatin and tannic acid in deionized water at 80°C in a mass ratio of 0.7:1, stir for two hours, and cool and shape the obtained precipitate to obtain the target hydrogel;
(2)原电池的构建(2) Construction of primary battery
将作为原电池负极材料的锌片和作为原电池正极材料的空气电极贴附于水凝胶两侧的两端，构成原电池；A galvanic battery is formed by attaching the zinc sheet as the negative electrode material of the galvanic battery and the air electrode as the positive electrode material of the galvanic battery on both ends of the hydrogel;
(3)自供能应变传感器的制备；(3) Preparation of self-powered strain sensor;
将100Ω定值电阻连接于原电池的正负极，定值电阻的两端为信号输出点，输出的信号为电压信号，即可实现自供能应变传感器的制备。The 100Ω fixed-value resistor is connected to the positive and negative electrodes of the primary battery, the two ends of the fixed-value resistor are signal output points, and the output signal is a voltage signal, and the preparation of the self-powered strain sensor can be realized.
实施例4Example 4
(1)水凝胶的制备(1) Preparation of hydrogel
将明胶和单宁酸以质量比为0.7:1的比例溶于80℃的去离子水中，搅拌两小时，将所得沉淀物冷却塑型即可得到目标水凝胶；Dissolve gelatin and tannic acid in deionized water at 80°C in a mass ratio of 0.7:1, stir for two hours, and cool and shape the obtained precipitate to obtain the target hydrogel;
(2)原电池的构建(2) Construction of primary battery
通过真空蒸镀的方式在水凝胶的一端镀上一层锌膜作为原电池的负极材料，将作为原电池正极材料的铜片贴附于水凝胶的另一端，构成原电池；A zinc film is plated on one end of the hydrogel by vacuum evaporation as the negative electrode material of the primary battery, and the copper sheet as the positive electrode material of the primary battery is attached to the other end of the hydrogel to form a primary battery;
(3)自供能应变传感器的制备；(3) Preparation of self-powered strain sensor;
将1kΩ定值电阻连接于原电池的正负极，定值电阻的两端为信号输出点，输出的信号为电压信号，即可实现自供能应变传感器的制备。The 1kΩ fixed-value resistor is connected to the positive and negative electrodes of the primary battery, the two ends of the fixed-value resistor are signal output points, and the output signal is a voltage signal, and the preparation of the self-powered strain sensor can be realized.
实施例5Example 5
(1)水凝胶的制备(1) Preparation of hydrogel
将明胶和单宁酸以质量比为0.5:1的比例溶于80℃的去离子水中，搅拌两小时，将所得沉淀物冷却塑型即可得到目标水凝胶；Dissolve gelatin and tannic acid in deionized water at 80°C in a mass ratio of 0.5:1, stir for two hours, and cool and shape the obtained precipitate to obtain the target hydrogel;
(2)原电池的构建(2) Construction of primary battery
通过真空蒸镀的方式在水凝胶的一端镀上一层锌膜作为原电池的负极材料，将作为原电池正极材料的空气电极贴附于水凝胶的另一端，构成原电池；A layer of zinc film is plated on one end of the hydrogel by vacuum evaporation as the negative electrode material of the primary battery, and the air electrode as the positive electrode material of the primary battery is attached to the other end of the hydrogel to form a primary battery;
(3)自供能应变传感器的制备；(3) Preparation of self-powered strain sensor;
将100Ω定值电阻连接于原电池的正负极，定值电阻的两端为信号输出点，输出的信号为电压信号，即可实现自供能应变传感器的制备。The 100Ω fixed-value resistor is connected to the positive and negative electrodes of the primary battery, the two ends of the fixed-value resistor are signal output points, and the output signal is a voltage signal, and the preparation of the self-powered strain sensor can be realized.
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