Preparation method and application of wireless passive hydrogen sensor

Abstract

The invention relates to the technical field of hydrogen utilization safety risk prevention and control, in particular to a preparation method of a wireless passive hydrogen sensor, which comprises the following steps: drawing a sensor pattern, and printing the sensor pattern on a copper-plated PI film through an ink-jet printer; then heating the copper-plated PI film on a heating table; the heated copper-plated PI film is put into a FeCl3 solution to be soaked until all exposed copper coatings are eroded; the inductance coil and the interdigital capacitor are connected with each other by using conductive silver paste to obtain a sensor electrode part; depositing a layer of tungsten trioxide film on the prepared sensor electrode; and immersing the sensor electrode deposited with the tungsten trioxide film into a solution of phenyl phosphoric acid and absolute ethyl alcohol at room temperature for growth, and drying to obtain the phenyl phosphoric acid modified tungsten trioxide wireless passive hydrogen sensor. The wireless passive hydrogen sensor is attached to the position where hydrogen is prone to leakage, hydrogen leakage is detected, and the problem of early warning of hydrogen leakage is solved.

Description

Technical Field

[0001] The present invention relates to the technical field of hydrogen utilization safety risk prevention and control, and in particular to a preparation method and application of a wireless passive hydrogen sensor. Background Art

[0002] With the accelerated construction of hydrogen energy supply stations, especially the development of hydrogen refueling stations from single hydrogen refueling stations to combined hydrogen refueling / gasoline (gas) and hydrogen refueling / charging stations, it is easy to form significant risk superposition and coupling effects in the event of an emergency. The country has put forward relevant requirements for ensuring the safety of the comprehensive utilization of hydrogen energy, requiring the promotion of the coordinated development of key core technologies and safety technologies in the hydrogen energy industry, and the active use of advanced technologies such as the Internet, big data, and artificial intelligence to timely warn of risk conditions such as leakage, fatigue, and deflagration in hydrogen energy production, storage, and transportation equipment, sites, and application terminals, effectively improving accident prevention capabilities. However, at this stage, my country's research on hydrogen energy focuses more on hydrogen production, hydrogen use, hydrogen storage materials, or production processes, and pays less attention to the safety risks of systemic leakage of hydrogen energy supply facilities such as hydrogen refueling stations. There are many gaps in the key technologies for early monitoring and early warning of safety risks of hydrogen facility leakage in the field of emergency management.

[0003] Patent application number CN202510078416.3 proposes a hydrogen explosion simulation system for hydrogen refueling stations under obstructed conditions, enabling the construction of a three-dimensional hydrogen refueling station model and explosion process simulation, but it lacks risk prediction and early warning capabilities. Patent application number CN202411830137.X also designs a hydrogen gas leak detection and early warning device. However, the device is too large to be installed, and the power supply requires an explosion-proof design. This also makes it difficult to flexibly establish a risk warning system network to build a coordinated disaster prevention and control chain.

[0004] A wireless passive hydrogen sensor with high efficiency, low cost and excellent performance has been invented. Its passive feature makes it more suitable for hydrogen leakage and explosion hazardous environments. The wireless method is more conducive to systematic and networked encrypted deployment in hydrogen energy supply facilities, forming an all-round, three-dimensional and dynamic hydrogen leakage detection equipment system and safety risk dynamic monitoring and early warning capabilities, establishing an early warning model for hydrogen leakage accidents, and forming a hydrogen safety "perception-assessment-warning-decision-making" integrated risk prevention and control technology, realizing the transformation from emergency response to a single disaster of hydrogen leakage to the complex evolution of disaster chains and their coordinated emergency response technologies. Summary of the Invention

[0005] The object of the present invention is to provide a method for preparing a wireless passive hydrogen sensor, which is simple and easy to operate, has low production cost, and the prepared sensor has high sensitivity.

[0006] To achieve the above object, the present invention provides a method for preparing a wireless passive hydrogen sensor, comprising the following steps:

[0007] Drawing a sensor pattern and printing the sensor pattern on a copper-coated PI film using an inkjet printer;

[0008] The copper-coated PI film after inkjet printing was heated on a heating table for 2 hours;

[0009] The heated copper-plated PI film is placed in a FeCl3 solution and immersed until all exposed copper coatings are corroded;

[0010] The inductor coil and the interdigital capacitor are connected to each other using conductive silver paste to obtain the sensor electrode part;

[0011] Depositing a tungsten trioxide film on the prepared sensor electrode;

[0012] The sensor electrode deposited with tungsten trioxide film was immersed in a solution of phenylphosphoric acid and anhydrous ethanol for 12 hours at room temperature. After drying, a phenylphosphoric acid-modified tungsten trioxide wireless passive hydrogen sensor was obtained.

[0013] The heated copper-plated PI film is immersed in a FeCl3 solution until all exposed copper coatings are corroded. The step further includes:

[0014] The concentration of FeCl3 solution is 3 mol / L.

[0015] Wherein, a tungsten trioxide film is deposited on the prepared sensor electrode, and the step further comprises:

[0016] Magnetron sputtering is used on the prepared sensor electrode with a sputtering power of 100 W and a deposition time of tungsten trioxide film for 3 minutes to obtain a tungsten trioxide film with a thickness of 200 nm.

[0017] The sensor electrode deposited with the tungsten trioxide film is immersed in a solution of phenylphosphoric acid and anhydrous ethanol at room temperature for 12 hours, and dried to obtain a phenylphosphoric acid-modified tungsten trioxide wireless passive hydrogen sensor. The steps further include:

[0018] The ratio of the amount of phenylphosphonic acid to the volume of anhydrous ethanol was 0.1 mmol:10 mL.

[0019] The sensor electrode deposited with the tungsten trioxide film is immersed in a solution of phenylphosphoric acid and anhydrous ethanol at room temperature for 12 hours, and dried to obtain a phenylphosphoric acid-modified tungsten trioxide wireless passive hydrogen sensor. The steps further include:

[0020] The growth time of phenyl phosphate molecules ranges from 10 to 36 hours, with the optimal growth time being 12 hours.

[0021] Among them, the application of the wireless passive hydrogen sensor prepared by the method is to attach the wireless passive hydrogen sensor to a place where hydrogen is likely to leak when detecting hydrogen leakage, place an interrogation antenna on the upper part of the wireless passive hydrogen sensor, and connect the interrogation antenna to a network analyzer to read the resonant frequency of the wireless passive hydrogen sensor. The presence of hydrogen leakage and the concentration of hydrogen leakage are dynamically reflected according to the offset of the resonant frequency.

[0022] The preparation method and application of a wireless passive hydrogen sensor of the present invention are simple and easy to operate, low in cost, and easy to achieve large-scale production. The prepared wireless passive hydrogen sensor has high sensitivity. When conducting hydrogen facility leak detection, the wireless passive hydrogen sensor is attached to a location where hydrogen is likely to leak, an interrogation antenna is placed above the wireless passive hydrogen sensor, and the interrogation antenna is connected to a network analyzer to read the resonant frequency of the wireless passive hydrogen sensor. The offset of the resonant frequency reflects whether there is a hydrogen leak and the concentration of the hydrogen leak, thereby solving the problem of early warning of hydrogen leaks. BRIEF DESCRIPTION OF THE DRAWINGS

[0023] In order to more clearly illustrate the specific embodiments of the present invention or the technical solutions in the prior art, the following briefly introduces the drawings required for use in the specific embodiments or the description of the prior art. Obviously, the drawings in the following description are some embodiments of the present invention.

[0024] Figure 1 The present invention is a flowchart of the steps of the preparation method of the wireless passive hydrogen sensor.

[0025] Figure 2 This is an exploded view of the wireless passive hydrogen sensor prepared by the present invention.

[0026] Figure 3 This is a physical picture of the wireless passive hydrogen sensor prepared by the present invention.

[0027] Figure 4 This is the frequency response of the sensor prepared by the present invention under different hydrogen concentrations.

[0028] Figure 5 This is a sensitivity analysis diagram of the wireless passive hydrogen sensor prepared by the present invention. DETAILED DESCRIPTION

[0029] The following describes embodiments of the present invention in detail, examples of which are shown in the accompanying drawings, wherein the same or similar reference numerals throughout represent the same or similar elements or elements having the same or similar functions. The embodiments described below with reference to the accompanying drawings are exemplary and are intended to be used to explain the present invention, and are not to be construed as limiting the present invention.

[0030] The first embodiment of this application is:

[0031] A method for preparing a wireless passive hydrogen sensor of the present invention comprises the following steps:

[0032] S101: drawing a sensor pattern and printing the sensor pattern on a copper-plated PI film using an inkjet printer;

[0033] S102: heating the copper-plated PI film after inkjet printing on a heating table for 2 hours;

[0034] S103: placing the heated copper-plated PI film in a FeCl3 solution and immersing it until all exposed copper coatings are corroded;

[0035] S104: Connecting the inductor coil and the interdigital capacitor to each other using conductive silver paste to obtain a sensor electrode portion;

[0036] S105: depositing a tungsten trioxide film on the prepared sensor electrode;

[0037] S106: Immerse the sensor electrode deposited with the tungsten trioxide film in a solution of phenylphosphoric acid and anhydrous ethanol for 12 hours at room temperature, and after drying, obtain a phenylphosphoric acid-modified tungsten trioxide wireless passive hydrogen sensor.

[0038] Specifically: first, the device pattern is drawn using AutoCAD software, and the pattern is printed on a copper-plated PI film using an inkjet printer; then the printed copper-plated PI film is placed on a heating table and heated for 2 hours. After heating, the patterned copper-plated PI film is immersed in a 3 mol / L FeCl3 solution until all exposed copper coatings of the copper-plated PI film are corroded; then the inductor coil and the interdigital capacitor are interconnected using conductive silver paste and placed on the PI film to obtain the sensor electrode part; then a layer of tungsten trioxide film with a thickness of 200 nm is deposited on the prepared sensor electrode by magnetron sputtering; finally, the sensor electrode deposited with the tungsten trioxide film is immersed in a mixed solution of phenyl phosphate and anhydrous ethanol at a volume ratio of 0.1 mmol: 10 mL at room temperature and allowed to stand for 12 hours for phenyl phosphate molecular growth. After drying, a phenyl phosphate molecule-modified tungsten oxide hydrogen sensor is obtained.

[0039] The preparation method of the wireless passive hydrogen sensor provided by the present invention is simple and easy to operate, has low cost, is easy to achieve large-scale production, and the prepared sensor has high sensitivity.

[0040] The second embodiment of this application is:

[0041] Based on the first example, the fabricated wireless passive hydrogen detection sensor is used for systematic, comprehensive leak detection in hydrogen facilities. First, the wireless passive hydrogen sensor is attached to a pre-identified hydrogen leak site. An interrogation antenna is placed above the sensor and connected to a network analyzer. The resonant frequency of the wireless passive hydrogen sensor is read. The shift in the resonant frequency indicates the presence of a hydrogen leak, the concentration of the leaked hydrogen, the location of the leak, and other information, enabling dynamic sensing of hydrogen leak risks.

[0042] The working principle of the wireless passive hydrogen sensor prepared by the preparation method provided by the present invention is as follows: the dielectric constant of the hydrogen-sensitive material phenyl phosphate molecule modified tungsten oxide changes significantly under different hydrogen concentrations, which can cause a significant frequency shift in the sensor's resonant frequency; the prepared wireless passive hydrogen sensor is placed in a test cavity under dynamic atmosphere conditions, and the interrogation antenna connected to the network analyzer is fixed above the sensor. Subsequently, hydrogen gas with concentrations of 0 ppm, 50 ppm, and 100 ppm is introduced into the cavity in sequence at a flow rate of 1000 sccm, and the introduction time of each concentration is 5 minutes. After the gas concentration stabilizes, the change in the resonant frequency of the wireless passive hydrogen sensor is recorded. The experimental results show that the resonant frequency shows a significant shift at different concentrations, and the sensitivity is 0.019 MHz / ppm, which verifies its excellent response performance and shows a high sensitivity detection of hydrogen concentration.

[0043] The calculation formula of hydrogen concentration detection sensitivity GF is:

[0044]

[0045] Among them, f gas is the resonant frequency of the sensor at a certain hydrogen concentration; f0 is the resonant frequency of the sensor at 40°C; δc is the difference between the gas concentration during the test and the initial concentration.

[0046] The above disclosure is merely one or more preferred embodiments of the present application and is not intended to limit the scope of the present application. A person skilled in the art will understand that all or part of the processes of the above embodiments and equivalent changes made in accordance with the claims of the present application are still within the scope of the present application.

Claims

1. A method for preparing a wireless passive hydrogen sensor, characterized in that: The following steps are involved: Drawing a sensor pattern and printing the sensor pattern on a copper-coated PI film using an inkjet printer; The copper-coated PI film after inkjet printing was heated on a heating table for 2 hours; The heated copper-plated PI film is placed in a FeCl3 solution and immersed until all exposed copper coatings are corroded; The inductor coil and the interdigital capacitor are connected to each other using conductive silver paste to obtain the sensor electrode part; Depositing a tungsten trioxide film on the prepared sensor electrode; The sensor electrode deposited with tungsten trioxide film was immersed in a solution of phenylphosphoric acid and anhydrous ethanol for 12 hours at room temperature, and then dried to obtain a phenylphosphoric acid-modified tungsten trioxide wireless passive hydrogen sensor.

2. The method for preparing a wireless passive hydrogen sensor according to claim 1, wherein: The heated copper-plated PI film is placed in a FeCl3 solution and immersed until all exposed copper coatings are corroded. The step further includes: The concentration of FeCl3 solution is 3 mol / L.

3. The method for preparing a wireless passive hydrogen sensor according to claim 1, wherein: Depositing a tungsten trioxide film on the prepared sensor electrode, the step further includes: Magnetron sputtering is used on the prepared sensor electrode with a sputtering power of 100 W and a deposition time of tungsten trioxide film for 3 minutes to obtain a tungsten trioxide film with a thickness of 200 nm.

4. The method for preparing a wireless passive hydrogen sensor according to claim 1, wherein: The sensor electrode deposited with the tungsten trioxide film is immersed in a solution of phenylphosphoric acid and anhydrous ethanol at room temperature for 12 hours, and dried to obtain a phenylphosphoric acid-modified tungsten trioxide wireless passive hydrogen sensor. The steps further include: The ratio of the amount of phenylphosphonic acid to the volume of anhydrous ethanol was 0.1 mmol:10 mL.

5. The method for preparing a wireless passive hydrogen sensor according to claim 1, wherein: The sensor electrode deposited with the tungsten trioxide film is immersed in a solution of phenylphosphoric acid and anhydrous ethanol at room temperature for 12 hours, and dried to obtain a phenylphosphoric acid-modified tungsten trioxide wireless passive hydrogen sensor. The steps further include: The growth time of phenyl phosphate molecules ranges from 10 to 36 hours, with the optimal growth time being 12 hours.

6. An application of a wireless passive hydrogen sensor prepared by the method according to any one of claims 1 to 5, characterized in that: When detecting hydrogen leaks, a wireless passive hydrogen sensor is attached to a location where hydrogen is likely to leak, an interrogation antenna is placed on top of the wireless passive hydrogen sensor, and the interrogation antenna is connected to a network analyzer to read the resonant frequency of the wireless passive hydrogen sensor. The offset of the resonant frequency is used to dynamically reflect whether there is a hydrogen leak and monitor the concentration of the hydrogen leak.

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