WO2022116355A1 - 一种自供能湿度传感器、制备方法及应用 - Google Patents

一种自供能湿度传感器、制备方法及应用 Download PDF

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WO2022116355A1
WO2022116355A1 PCT/CN2020/142183 CN2020142183W WO2022116355A1 WO 2022116355 A1 WO2022116355 A1 WO 2022116355A1 CN 2020142183 W CN2020142183 W CN 2020142183W WO 2022116355 A1 WO2022116355 A1 WO 2022116355A1
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self
humidity sensor
fiber membrane
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hydrophilic fiber
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戴建国
李晓强
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江苏波司登科技有限公司
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    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
    • G01N21/75—Systems in which material is subjected to a chemical reaction, the progress or the result of the reaction being investigated
    • G01N21/77—Systems in which material is subjected to a chemical reaction, the progress or the result of the reaction being investigated by observing the effect on a chemical indicator
    • G01N21/78—Systems in which material is subjected to a chemical reaction, the progress or the result of the reaction being investigated by observing the effect on a chemical indicator producing a change of colour
    • G01N21/81—Indicating humidity
    • H—ELECTRICITY
    • H02—GENERATION; CONVERSION OR DISTRIBUTION OF ELECTRIC POWER
    • H02N—ELECTRIC MACHINES NOT OTHERWISE PROVIDED FOR
    • H02N3/00—Generators in which thermal or kinetic energy is converted into electrical energy by ionisation of a fluid and removal of the charge therefrom
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
    • G01N21/75—Systems in which material is subjected to a chemical reaction, the progress or the result of the reaction being investigated
    • G01N2021/758—Systems in which material is subjected to a chemical reaction, the progress or the result of the reaction being investigated using reversible reaction

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  • the invention relates to a humidity sensor, preparation method and application, in particular to a self-powered humidity sensor, preparation method and application.
  • High-range humidity control is becoming more and more important in the fields of environmental protection, technological processes, scientific research and development, natural gas processing, healthcare, pharmaceutical industry, semiconductors, etc.
  • the use of humidity sensors with high sensitivity, wide range, good conductivity and low cost for daily applications can easily help people obtain more information, which is of great significance for monitoring sleep apnea, exercise frequency tracking and other applications.
  • various types of humidity sensors have been widely studied, including resistance, capacitance, quartz crystal micro- Balance (QCM) and voltage type, etc.
  • the task of the present invention is to provide a self-powered humidity sensor and a preparation method of the self-powered humidity sensor, so as to obtain a low-cost humidity sensor with simple preparation operation steps.
  • a self-powered humidity sensor includes a hydrophilic fiber membrane, a transparent insulating layer is attached to the back of the hydrophilic fiber membrane, and two parallel conductive tapes are attached to the front of the hydrophilic fiber membrane, The conductive tape is drawn out as an electrode, and the hydrophilic fiber membrane is soaked in a cobalt chloride solution and dried.
  • the distance between the conductive tapes is 0.2-2 mm.
  • the transparent insulating layer is a PET layer.
  • a preparation method of a self-powered humidity sensor comprising the following steps:
  • the mass fraction of the cobalt chloride aqueous solution is 2-20%.
  • the hydrophilic fiber membrane is soaked in the cobalt chloride aqueous solution for more than 6 hours at room temperature.
  • the blast drying temperature is 50-80°C.
  • the distance between the conductive tapes is 0.2-2 mm.
  • the above self-powered humidity sensor is used in the fields of anti-counterfeiting, functional fibers, clothing, humidity sensors and wearable functions.
  • the present invention has the advantages that the self-powered humidity sensor constructed by the cobalt chloride modified fiber membrane has the advantages of simple operation and low cost in the preparation process, and the prepared self-powered humidity sensor has high flexibility, reversible discoloration, and electrical conductivity. Good performance and so on.
  • the method of the invention by controlling the mass fraction of the cobalt chloride aqueous solution, the color depth of the cobalt chloride modified fiber membrane can be regulated, and the change of the environmental humidity can regulate the red and blue color changes of the sensor.
  • the obtained self-powered humidity sensor can be applied to a wide range of humidity environments (RH11-100%), and will show a phenomenon of changing from blue to red, and this change is reversible.
  • the self-powered humidity sensor has high humidity. Sensitivity, the maximum current can reach more than 6 000nA.
  • Figure 1 is a schematic structural diagram of a self-powered humidity sensor.
  • FIG. 2 is a voltage diagram of an embodiment self-powered humidity sensor at different humidity levels.
  • the performance of the self-powered humidity sensor obtained by soaking the hydrophilic fiber membrane with different concentrations of cobalt chloride solution is tested.
  • the reflection spectrum and color development photos of the obtained cobalt chloride modified fiber membrane were tested by a computer color matching instrument;
  • the The electrochemical workstation conducts current test on the composed self-powered humidity sensor, and uses a digital multimeter to measure its open-circuit voltage. The results of the performance tests are shown in the table below:
  • the fiber membrane modified by cobalt chloride has higher humidity sensitivity than the original in a high humidity environment (relative humidity 98%), and the higher the cobalt chloride concentration, the more obvious the response. Therefore, the self-powered humidity sensor can adjust the concentration of cobalt chloride according to different needs, making it more flexible and convenient in practical applications.
  • Fig. 2 is a self-powered humidity sensor prepared by adopting the hydrophilic fiber membrane obtained in Example 5 of the above table. At room temperature of 25° C., the dry self-powered humidity sensor is placed in different humidity environments (relative humidity is 11% ⁇ 33% ⁇ 59% ⁇ 75% ⁇ 98%), when the voltage remains stable, record the voltage curve for the next minute. As can be seen from Figure 2, in a high humidity environment (98% relative humidity), the self-powered humidity sensor can generate an open circuit voltage of 206mV.

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Abstract

一种自供能湿度传感器及其制备方法和应用，自供能湿度传感器包括亲水纤维膜（1），亲水纤维膜（1）的背面粘贴透明隔绝层（3），亲水纤维膜（1）的正面粘贴两条平行的导电胶带（2），由导电胶带（2）作为电极引出，亲水纤维膜（1）进行浸泡氯化钴溶液并烘干处理。制备方法操作简单，成本低，制得的自供能湿度传感器适用于宽湿度范围环境，且具备高湿敏性。

Description

一种自供能湿度传感器、制备方法及应用 技术领域
本发明涉及一种湿度传感器、制备方法及应用，特别是涉及一种自供能湿度传感器、制备方法及应用。
背景技术
近年来，包括智能移动设备和微机电系统(MEMS)在内的可穿戴和柔性电子技术得到了蓬勃发展，在下一代电子产品中具有广阔的应用前景。然而，它们中的大多数是由需要定期充电和最终更换的电池供电，这将导致环境问题和复杂的管理问题。为了应对这个问题，一系列基于摩擦电、压电、和热电效应的先进能源发电技术正在开发中，以直接从环境中获取清洁能源。而水蒸气或湿气，一种广泛存在于地球和生物有机体中的巨大资源，已被作为一种新的可收获能源被开发用来发电。
高范围的湿度控制在环境保护、工艺流程、科学研究与开发、天然气加工、医疗保健、医药工业、半导体等领域变得越来越重要。而利用灵敏度高、范围广、导电性能好、成本低的湿度传感器，进行生活化的应用，简便地帮助人们获取更多的信息，对监测睡眠呼吸暂停、运动频率追踪等应用具有重要意义。目前，基于与空气中的水分子相互作用后一些相关物理参数(如电阻、电容、频率、电压等)的变化，人们广泛研究了各种器件类型的湿度传感器，包括电阻、电容、石英晶体微天平(QCM)和电压类型等。
在此背景下，先前的研究报告了多孔碳中蒸发诱导水流相关的恒定电压的出现，但输出电压较低，导致这种效应的物理/化学机制仍不确定。水分的扩散也被证明可以从氧化石墨烯中发电，但需要在恒定电场下进行预极化。另外，很多湿度传感器的制备过程通常涉及复杂的微纳结构材料的合成路线、先进的器件组装工艺，因此制备成本居高不下。
发明内容
针对上述现有技术缺陷，本发明的任务在于提供一种自供能湿度传感器，及提供一种自供能湿度传感器的制备方法，以简单的制备操作步骤获得低成本湿度传感器。
本发明技术方案是这样的：一种自供能湿度传感器，包括亲水纤维膜，所述亲水纤维膜的背面粘贴透明隔绝层，所述亲水纤维膜的正面粘贴两条平行的导电胶带，由所述导电胶带作为电极引出，所述亲水纤维膜进行浸泡氯化钴溶液并烘干处理。
优选地，所述导电胶带的间距为0.2～2mm。
优选地，所述透明隔绝层为PET层。
一种自供能湿度传感器的制备方法，包括以下步骤：
(1)配制氯化钴水溶液：在室温下称量一定比例的六水和氯化钴晶体，使用去离子水混合，搅拌使其溶解均匀；
(2)亲水性纤维膜的改性：将亲水性纤维膜在配置好的氯化钴水溶液中充分浸泡后，使氯化钴溶液附着于纤维膜的孔隙中；然后，将湿润的纤维膜平铺于烘箱中鼓风干燥，进行水分蒸发诱导纤维素链的致密堆积，氯化钴晶体密集集合于纤维膜的孔隙中，得到蓝色的氯化钴改性纤维膜；
(3)制成自供能湿度传感器：将改性后的亲水性纤维膜裁成矩形，一面粘贴两条平行的聚酯导电胶带，形成两个电极；另一面使用透明PET封住底面，隔绝空气和其他。最后，得到自供能湿度传感器。
优选地，所述氯化钴水溶液的质量分数为2～20％。
优选地，所述亲水性纤维膜在所述氯化钴水溶液中浸泡是在室温条件下浸泡6小时以上。
优选地，所述鼓风干燥温度为50～80℃。
优选地，所述导电胶带的间距为0.2～2mm。
上述自供能湿度传感器应用于防伪、功能性的纤维、服装、湿度传感器和可穿戴功能领域。
本发明与现有技术相比的优点在于：由氯化钴改性纤维膜构建的自供能湿度传感器，制备过程操作简单、成本低，制得的自供能湿度传感器具有高柔性、变色可逆、导电性能好等优点。本发明方法，通过控制氯化钴水溶液的质量分数，可调控氯化钴改性纤维膜的颜色深浅，环境湿度的变化可调控传感器的进行红蓝颜色变化。制得的自供能湿度传感器，可适用于宽范围的湿度环境(RH11～100％)，会呈现由蓝色变为红色的现象，且这种变化是可逆的，该自供能湿度传感器具有高湿敏性，最高电流可达6 000nA以上。
附图说明
图1为自供能湿度传感器结构示意图。
图2为实施例自供能湿度传感器在不同湿度下的电压图。
具体实施方式
下面结合实施例对本发明作进一步说明，但不作为对本发明的限定。
本实施例涉及的自供能湿度传感器的制备方法如下：
(1)配制氯化钴水溶液：在室温25℃下，称量一定比例的六水和氯化钴晶体，使用去离子水混合配置50ml的氯化钴水溶液，均匀搅拌30分钟使其充分融合，静置1小时以 完全消除气泡，全程密闭保存。
(2)亲水性纤维膜的改性：将亲水性纤维膜浸泡在上述制备的氯化钴水溶液中6小时及以上，使氯化钴溶液附着于纤维膜的孔隙中；然后，将湿润的纤维膜平铺于烘箱中以50～80℃本实施例为60℃鼓风干燥1小时，进行水分蒸发诱导纤维素链的致密堆积，氯化钴晶体密集集合于纤维膜的孔隙中，得到蓝色的氯化钴改性纤维膜。
(3)制成自供能湿度传感器：将改性后的亲水性纤维膜裁成矩形，一面粘贴两条平行的聚酯导电胶带，形成两个电极，两条聚酯导电胶带的间距可以是0.2～2mm，本实施例采用1mm间距；另一面使用透明PET封住底面，隔绝空气和其他，制得自供能湿度传感器。自供能湿度传感器的结构如图1所示，氯化钴改性的亲水纤维膜1的正面粘贴两条平行的导电胶带2，由导电胶带2作为电极引出，亲水纤维膜1的背面是以PET层3为透明隔绝层进行封闭。
本实施例对采用不同浓度的氯化钴溶液浸泡亲水性纤维膜得到的自供能湿度传感器进行性能测试。为了测定氯化钴改性纤维膜的变色性能，采用电脑配色仪对得到的氯化钴改性纤维膜进行反射光谱和显色照片测试；为了测定氯化钴改性纤维膜的电学性能，采用电化学工作站对组成的自供能湿度传感器进行电流测试，采用数字万用表测定其开路电压。性能测试的结果如下表所示：
Figure PCTCN2020142183-appb-000001
由该表可知，经过氯化钴改性后的纤维膜在高湿度环境下(相对湿度98％)都有高于原来的湿敏性能，且氯化钴浓度越高，响应越明显。因此，该自供能湿度传感器可以根据不同的需求，调控氯化钴浓度，使其在实际应用中更加灵活和便捷。
图2为采用上表的实施例方案5得到的亲水性纤维膜制备的自供能湿度传感器，在室温25℃下，将干燥的自供能湿度传感器置于不同的湿度环境(相对湿度为11％～33％～59％～75％～98％)中，当电压保持稳定时，记录下一分钟的电压曲线。由图2可知，在高湿度环境下(相对湿度98％)，该自供能湿度传感器可产生206mV的开路电 压。

Claims (10)

  1. 一种自供能湿度传感器，其特征在于，包括亲水纤维膜，所述亲水纤维膜的背面粘贴透明隔绝层，所述亲水纤维膜的正面粘贴两条平行的导电胶带，由所述导电胶带作为电极引出，所述亲水纤维膜进行浸泡氯化钴溶液并烘干处理。
  2. 根据权利要求1所述的自供能湿度传感器，其特征在于，所述导电胶带的间距为0.2～2mm。
  3. 根据权利要求1所述的自供能湿度传感器，其特征在于，所述透明隔绝层为PET层。
  4. 一种自供能湿度传感器的制备方法，其特征在于，包括以下步骤：(1)配制氯化钴水溶液；(2)亲水性纤维膜的改性：将亲水性纤维膜在配置好的氯化钴水溶液中充分浸泡后平铺进行鼓风干燥，得到氯化钴改性纤维膜；(3)将改性后的亲水性纤维膜裁成需要的形状，一面粘贴两条平行的聚酯导电胶带，形成两个电极；另一面粘贴透明隔绝层，隔绝空气和其他，得到自供能湿度传感器。
  5. 根据权利要求4所述的自供能湿度传感器的制备方法，其特征在于，所述氯化钴水溶液的质量分数为2～20％。
  6. 根据权利要求4所述的自供能湿度传感器的制备方法，其特征在于，所述亲水性纤维膜在所述氯化钴水溶液中浸泡是在室温条件下浸泡6小时以上。
  7. 根据权利要求4所述的自供能湿度传感器的制备方法，其特征在于，所述鼓风干燥温度为50～80℃。
  8. 根据权利要求4所述的自供能湿度传感器的制备方法，其特征在于，所述聚酯导电胶带的间距为0.2～2mm。
  9. 根据权利要求4所述的自供能湿度传感器的制备方法，其特征在于，所述透明隔绝层为PET层。
  10. 根据权利要求1所述的自供能湿度传感器在防伪、功能性的纤维、服装、湿度传感器和可穿戴功能领域的应用。
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