Humidity gating device and manufacturing method thereof, and medicine moisture wireless monitoring equipment

Abstract

The invention provides a humidity gating device, a manufacturing method of the humidity gating device and medicine moisture wireless monitoring equipment, and belongs to the technical field of electronic materials and devices. The humidity gating device includes: a substrate; the positive electrode and the negative electrode are respectively positioned on the same surface of the substrate, and a gap is formed between the positive electrode and the negative electrode; at least part of the solid electrolyte is located in the gap, the solid electrolyte is connected with the positive electrode and the negative electrode, and the ionic conductivity of the solid electrolyte changes in response to the humidity change of the environment to be detected; wherein in response to the change of the ionic conductivity of the solid electrolyte affected by humidity, the electric signals output by the positive electrode and the negative electrode change, and the electric signals are used for representing the humidity of the environment to be measured. The humidity gating device is applied to the medicine moisture wireless monitoring equipment and can accurately measure the medicine moisture in real time.

Description

Technical Field

[0001] This invention relates to the field of electronic materials and devices, and in particular to a humidity gating device and its manufacturing method, and a wireless moisture monitoring device for pharmaceuticals. Background Technology

[0002] In the pharmaceutical field, drugs are crucial for disease prevention, treatment, and diagnosis, and their quality directly impacts patient health and safety. Drug stability is a core element in ensuring drug quality, determined by the drug's inherent physicochemical properties but also significantly affected by the external environment, with humidity being particularly critical. In high-humidity environments, drugs are prone to hygroscopic and deliquescent changes, leading to chemical degradation, harmful impurities, decreased active ingredient content, weakened efficacy, and even increased toxicity risks, seriously jeopardizing drug safety and efficacy. Furthermore, abnormal humidity can alter a drug's appearance, solubility, and bioavailability, and even shorten its shelf life. Therefore, in-depth understanding and effective monitoring of drug moisture changes during research, development, production, storage, and distribution are of paramount importance for quality control and shelf-life determination, thereby ensuring medication safety. Summary of the Invention

[0003] In view of this, the present invention provides a humidity gating device and its manufacturing method, and a wireless drug moisture monitoring device, which includes a humidity gating device and can monitor drug moisture in real time.

[0004] According to one embodiment of the present invention, a humidity gating device is provided, comprising:

[0005] A substrate; a positive electrode and a negative electrode, respectively located on the same surface of the substrate, with a gap between the positive electrode and the negative electrode; a solid electrolyte, at least partially located within the gap, and connected to the positive electrode and the negative electrode respectively, wherein the ionic conductivity of the solid electrolyte changes in response to changes in the humidity of the test environment; wherein, in response to changes in the ionic conductivity of the solid electrolyte affected by humidity, the electrical signals output by the positive electrode and the negative electrode change, and the electrical signals are used to characterize the humidity of the test environment.

[0006] According to another embodiment of the present invention, a method for manufacturing a humidity gating device is provided, comprising:

[0007] Preparation of solid electrolyte slurry;

[0008] Positive electrode slurry and negative electrode slurry were prepared separately;

[0009] A first inert conductive metal layer and a second inert conductive metal layer are respectively bonded to a substrate. A positive electrode paste and a negative electrode paste are respectively drop-coated onto the first inert conductive metal layer and the second inert conductive metal layer to form a positive electrode and a negative electrode on the substrate, respectively.

[0010] Solid electrolyte slurry is drop-coated onto the positive and negative electrodes respectively, and then dried to obtain solid electrolyte, wherein the solid electrolyte is connected to the positive and negative electrodes respectively.

[0011] According to another embodiment of the present invention, a wireless moisture monitoring device for pharmaceuticals is provided, comprising:

[0012] A container suitable for holding the medicine to be tested;

[0013] A heating platform is used to heat the medicine to be tested. The container is placed on the heating platform.

[0014] The humidity gating device mentioned above, when placed inside a container, is suitable for outputting an electrical signal based on the humidity inside the container;

[0015] The external circuit wires are respectively connected to the positive and negative electrodes of the humidity gate device, and are suitable for transmitting the electrical signal output by the humidity gate device to the electrical signal receiving device.

[0016] An electrical signal receiving device, including a wireless Bluetooth module, is suitable for transmitting electrical signals to mobile devices.

[0017] According to the humidity-gated device provided in the above embodiments of the present invention, the device can quickly respond to changes in ambient humidity, efficiently convert humidity signals into current signals, achieve self-powered operation, and exhibit excellent performance such as high stability, high sensitivity, and intrinsic flexibility. Specifically, the self-powered characteristic of the device is driven by the potential difference between the positive and negative electrodes to generate energy. Its high stability is based on the excellent hygroscopic and dehumidifying properties of the solid electrolyte, thereby enabling the device to maintain stable performance with almost no degradation during 200 cycle tests. The high sensitivity stems from the humidity-sensitive characteristics of the solid electrolyte; under the influence of humidity changes, its ionic conductivity changes rapidly, with corresponding response and recovery rates both exceeding 1000 nA / s. The intrinsic flexibility of the device is imparted by the polymer contained in the solid electrolyte, significantly enhancing its flexibility.

[0018] The wireless drug moisture monitoring device provided in the above embodiments of the present invention can monitor the moisture content of drugs in real time. Attached Figure Description

[0019] To more clearly illustrate the technical solutions of the embodiments of the present invention, the accompanying drawings of the embodiments will be briefly described below. Obviously, the drawings described below only relate to some embodiments of the present invention and are not intended to limit the present invention.

[0020] Figure 1 This is a schematic diagram of the humidity gating device provided in an embodiment of the present invention;

[0021] Figure 2 This is a schematic diagram of the structure of the wireless moisture monitoring device for pharmaceuticals provided in an embodiment of the present invention;

[0022] Figure 3 This is a scanning electron microscope image of the positive electrode provided in Embodiment 1 of the present invention;

[0023] Figure 4 This is a scanning electron microscope image of the negative electrode provided in Embodiment 1 of the present invention;

[0024] Figure 5 The response / recovery curve of the humidity gating device provided in Embodiment 1 of the present invention is shown in a single test.

[0025] Figure 6 The response / recovery curve of the humidity gating device provided in Embodiment 1 of the present invention after 200 cycles;

[0026] Figure 7 The current curves for different drug moisture contents identified by the wireless drug moisture monitoring device provided in Embodiment 1 of the present invention;

[0027] Figure 8 The response / recovery curve of the humidity gating device provided in Embodiment 2 of the present invention is shown below.

[0028] Figure 9 Scanning electron microscope images of HOF-BTB nanoribbon structures under different NaCl solution addition amounts provided in embodiments of the present invention;

[0029] Figure 10 A comparison chart of the response / recovery speed and on / off ratio of humidity gating devices prepared with different NaCl solution addition amounts provided in the embodiments of the present invention;

[0030] Figure 11 Scanning electron microscope (SEM) images of HOF-BTB nanoribbon structures under different PVA solution addition amounts provided in embodiments of the present invention; and

[0031] Figure 12 A comparison chart of the response / recovery speed and on / off ratio of humidity gating devices prepared with different amounts of PVA solution added according to embodiments of the present invention.

[0032] Explanation of reference numerals in the attached figures:

[0033] 1-Base;

[0034] 2-Positive electrode;

[0035] 3-Negative electrode;

[0036] 4-Solid electrolyte. Detailed Implementation

[0037] To make the objectives, technical solutions, and advantages of this invention clearer, the invention will be further described in detail below with reference to specific embodiments and the accompanying drawings. However, this invention can be implemented in different forms and should not be construed as limited to the embodiments set forth herein. Rather, these embodiments are provided to make the invention thorough and complete, and to fully convey the scope of the invention to those skilled in the art. In the accompanying drawings, for clarity, the dimensions and relative dimensions of layers and regions may be exaggerated, and the same reference numerals denote the same elements throughout.

[0038] The terminology used herein is for the purpose of describing particular embodiments only and is not intended to limit the invention. The terms “comprising,” “including,” etc., as used herein indicate the presence of the stated features, steps, operations, and / or components, but do not exclude the presence or addition of one or more other features, steps, operations, or components.

[0039] Among related technologies, commonly used methods for determining and monitoring the moisture content of pharmaceuticals mainly include: Karl Fischer titration, loss on drying, and sensor monitoring technology.

[0040] Karl Fischer titration involves a quantitative redox reaction between water and an iodine-sulfur dioxide-pyridine-methanol system. The water content of the sample is then determined by titration using either electrophoresis or volumetric methods. While this method offers high precision, it requires frequent instrument calibration, demands a high level of operator skill, and presents significant operational challenges. Furthermore, the reagents used in the test—pyridine, methanol, and sulfur dioxide—are all toxic, posing a considerable health hazard to the test personnel.

[0041] The loss on drying method involves drying the sample at a constant weight at a specified temperature and calculating the volatile water content based on the mass difference. However, this method is cumbersome, requires large sample sizes (typically 1-2g), and necessitates damaging the packaging, making it unsuitable for non-destructive monitoring of pharmaceuticals. Furthermore, neither Karl Fischer titration nor the loss on drying method provides real-time monitoring of pharmaceutical moisture content; both require partial testing, resulting in a delay. Additionally, both methods involve relatively complex procedures, increasing labor costs for staff.

[0042] Humidity sensing technology primarily relies on resistive, capacitive, and electrolyte humidity sensors. Typically, a humidity probe is inserted into the packaging or placed in the top space of the container to collect relative humidity data in real time. The humidity signal is then uploaded to a terminal via a wired or wireless module. This method does not require damaging the packaging, offers fast response, low cost, and can continuously record moisture dynamics, providing time-series data for stability studies. However, its key bottleneck lies in the design and development of high-performance humidity-sensing core components (humidity gating devices), which still require breakthroughs.

[0043] Humidity-gated devices mainly include resistive, capacitive, and quartz oscillator types. Related technologies employ a peeling process to fabricate interdigitated electrodes and a drop-coating method to prepare a chitosan-based composite humidity-sensitive film to construct a capacitively gated device for humidity response testing; however, the stability of this device needs improvement. Related research uses a mixed dispersion of tungsten disulfide and graphene oxide quantum dots as a humidity-sensitive film, detecting changes in external humidity by detecting corresponding resistance changes; however, this device is not self-driven and requires external power, increasing monitoring costs. Related research utilizes the abundant oxygen vacancies on the surface of copper oxide nanofibers to adsorb water molecules, thereby effectively changing the surface mass load of a quartz crystal microbalance to achieve humidity monitoring; however, this device is large and lacks flexibility, making it unsuitable for integration into small containers for pharmaceutical moisture monitoring.

[0044] Therefore, there is an urgent need to develop new humidity-gated devices that combine high stability, fast response, intrinsic flexibility, and self-powered characteristics to replace traditional humidity-sensitive elements; and to build a wireless sensing system based on these devices to achieve real-time, in-situ, and high-precision monitoring of moisture within the drug packaging system, so as to more effectively ensure drug quality and medication safety.

[0045] In view of this, and addressing the shortcomings and improvement needs of existing sensing and monitoring technologies for drug moisture determination and monitoring, this invention proposes a wireless drug moisture monitoring device based on a novel humidity-gated device. This device uses a humidity-gated device as its core humidity-sensitive element and is specifically designed to meet the high requirements of rapid response, high stability, and ease of operation for humidity-sensitive elements in wireless monitors used in drug moisture monitoring. The wireless monitoring device assembled using this novel humidity-gated device effectively solves the technical bottlenecks of existing technologies, such as monitoring delay, low measurement accuracy, and cumbersome monitoring procedures, significantly improving the real-time performance, accuracy, and convenience of drug moisture monitoring.

[0046] Figure 1 This is a schematic diagram of the humidity gating device provided in an embodiment of the present invention.

[0047] According to an exemplary embodiment of the present invention, the present invention provides a humidity gating device, with reference to... Figure 1 As shown, it includes:

[0048] Base 1;

[0049] Positive electrode 2 and negative electrode 3 are located on the same surface of substrate 1, and there is a gap between positive electrode 2 and negative electrode 3;

[0050] The solid electrolyte 4 is at least partially located in the voids and is connected to the positive electrode 2 and the negative electrode 3 respectively. The ionic conductivity of the solid electrolyte 4 changes in response to the change in humidity of the test environment.

[0051] In response to the change in the ionic conductivity of the solid electrolyte 4 affected by humidity, the electrical signals output by the positive electrode 1 and the negative electrode 2 change, and the electrical signals are used to characterize the humidity of the environment under test.

[0052] In an embodiment of the present invention, the material of the substrate 1 is a flexible insulating material.

[0053] In some embodiments, the flexible insulating material includes at least one of polyethylene terephthalate (PET) plastic sheets and polyimide (PI) plastic sheets.

[0054] In embodiments of the present invention, the solid electrolyte 4 comprises a hydrogen-bonded organic framework, a polymer, and metal ions confined by the hydrogen-bonded organic framework.

[0055] In some embodiments, the monomers forming the hydrogen-bonded organic framework (HOF) include, but are not limited to, 1,3,5-tris(4-carboxyphenyl)benzene (BTB), 1,2,4,5-tetra(4-carboxyphenyl)benzene (H4TCPB), and N,N,N',N'-tetra(p-aminophenyl)p-phenylenediamine (TAPD).

[0056] In some embodiments, the polymers include, but are not limited to, bacterial cellulose (BC) and polyvinyl alcohol (PVA).

[0057] In some embodiments, the metal ions confined by the hydrogen-bonded organic framework originate from an ionic solution, which includes, but is not limited to, NaCl solution and KCl solution.

[0058] In some embodiments, the concentration of the ionic solution is 1 to 5 mol / L, for example, 1 mol / L, 2 mol / L, 3 mol / L, 4 mol / L, 5 mol / L, but is not limited to the values ​​mentioned.

[0059] In embodiments of the present invention, the molar ratio of the hydrogen-bonded organic framework, the polymer, and the ionic solution is (1~5):(0.01~0.1):(0.02~0.1), for example 1:0.01:0.03, 2:0.01:0.05, 1:0.02:0.05, 1:0.02:0.02, 1:0.01:0.02, but is not limited to the values ​​listed.

[0060] The molar ratio of hydrogen-bonded organic framework to polymer is, for example, (1~5):(0.01~0.1). If the ratio is too small (e.g., less than 1:0.1), i.e., the polymer is excessive, it will block the membrane pores of the solid electrolyte, significantly reducing its porosity, leading to a decrease in the ion mobility of the solid electrolyte, and thus a decline in the electrochemical performance of the fabricated device. If the ratio is too large (e.g., greater than 5:0.01), i.e., the hydrogen-bonded organic framework is excessive, it will result in poor mechanical properties of the solid electrolyte, making it prone to breakage. Ion transport will encounter interruptions, resulting in slower or blocked migration speeds, and thus a decline in the performance (response / recovery rate, on / off ratio) of the fabricated device.

[0061] The molar ratio of hydrogen-bonded organic framework to ionic solution is, for example, (1~5):(0.02~0.1). If the ratio is too small (e.g., less than 1:0.1), meaning there is an excess of ionic solution, it will reduce the dehydration performance of the solid electrolyte, leading to a decrease in the electrochemical performance of the device. If the ratio is too large (e.g., greater than 5:0.02), meaning there is an excess of hydrogen-bonded organic framework, it will reduce the water absorption performance of the solid electrolyte, leading to a decrease in the electrochemical performance of the device.

[0062] In an embodiment of the present invention, the positive electrode 2 includes a positively charged functional material loaded on a first inert conductive metal layer, and the first inert conductive metal layer is loaded on a substrate 1.

[0063] In some embodiments, positively charged functional coatings include, but are not limited to, aminated carbon nanotubes and aminated graphene.

[0064] In an embodiment of the present invention, the negative electrode comprises a negatively charged functional material loaded on a second inert conductive metal layer, and the second inert conductive metal layer is loaded on a substrate 1.

[0065] In some embodiments, the negatively charged functional coatings include, but are not limited to, carboxylated carbon nanotubes and AgCl slurry.

[0066] In some embodiments, the first inert metal conductive layer and the second inert metal conductive layer are, for example, independently selected from at least one of Cu, Ag, Au, and Ti. The thickness of both the first and second inert metal conductive layers is, for example, 0.02 mm, a small thickness to ensure that the manufactured device is flexible.

[0067] In some embodiments, when preparing the positive electrode, the addition range of aminated nanotubes is 30-40 mg. Excessive addition will damage the flexible structure of the electrode and make it impossible to uniformly drop onto the first inert metal conductive layer (e.g., Ti sheet). Insufficient addition will result in poor conductivity.

[0068] In some embodiments, when preparing the negative electrode, the addition range of carboxylated nanotubes is 30-40 mg. Excessive addition will damage the flexible structure of the electrode and make it impossible to uniformly drop onto the second inert metal conductive layer (e.g., Ti sheet). Insufficient addition will result in poor conductivity.

[0069] According to an exemplary embodiment of the present invention, the present invention provides a method for manufacturing a humidity gating device, comprising: operations S1 to S4.

[0070] Operation S1 is used to prepare a solid electrolyte slurry.

[0071] In an embodiment of the present invention, the preparation of a solid electrolyte slurry includes: mixing an ionic solution with a hydrogen-bonded organic framework suspension and stirring thoroughly to obtain an ion-confined hydrogen-bonded organic framework suspension; and mixing the ion-confined hydrogen-bonded organic framework suspension with a polymer and stirring to obtain a solid electrolyte slurry.

[0072] In an embodiment of the present invention, the preparation of the hydrogen-bonded organic framework suspension includes: dissolving the hydrogen-bonded organic framework monomer in N,N-dimethylformamide and obtaining a clear solution by sonication; adding water to the clear solution and stirring at room temperature to obtain a homogeneous colloidal suspension of the hydrogen-bonded organic framework; washing the homogeneous colloidal suspension of the hydrogen-bonded organic framework with water; filtering using a 0.45 μm aqueous membrane; and finally dissolving the filter material in water to form the hydrogen-bonded organic framework suspension.

[0073] In some embodiments, the raw materials for preparing the solid electrolyte include hydrogen-bonded organic framework HOF-BTB, polyvinyl alcohol (PVA), and NaCl solution.

[0074] In some embodiments, the preparation of the hydrogen-bonded organic framework HOF-BTB includes: dissolving BTB (30-300 mg) in N,N-dimethylformamide (DMF, 5-50 mL) and obtaining a clear solution by sonication for 10 min. Next, 5-10 mol of water is added to the above solution. After stirring at room temperature for 5-10 h, a uniform colloidal suspension of HOF-BTB nanosheets is obtained. Another 5-10 mol of water is added to wash the suspension, which is then filtered using a 0.45 μm aqueous membrane. Finally, the filtrate is dissolved in water to form the HOF-BTB suspension.

[0075] In embodiments of the present invention, adding too much or too little DMF will disrupt the hydrogen-bonded organic framework structure.

[0076] In an embodiment of the present invention, 5-10 ml of 1-2 mg / ml HOF-BTB suspension was placed in a beaker; a NaCl solution with a concentration of 1-5 mol / L was prepared; 100-500 μL of the prepared NaCl solution was mixed with the HOF-BTB suspension; and the mixture was stirred thoroughly for 1 h to successfully prepare 1-2 mg / ml HOF-BTB with ion confinement (introducing hydrophilic sites).

[0077] In an embodiment of the present invention, the preparation of the solid electrolyte includes taking 5-10 ml of HOF-BTB suspension with introduced hydrophilic sites; taking 1-5 ml of 1% PVA solution; mixing the two solutions thoroughly and stirring for 1 h to obtain a solid electrolyte slurry.

[0078] Operation S2 is used to prepare positive electrode slurry and negative electrode slurry respectively.

[0079] In an embodiment of the present invention, the preparation of the positive electrode slurry includes: mixing a positively charged functional material and polyvinylidene fluoride and then grinding them to obtain a first mixture; adding N-methylpyrrolidone to the first mixture and grinding it to obtain the positive electrode slurry.

[0080] In some embodiments, aminated carbon nanotubes (50-100 mg) and polyvinylidene fluoride (PVDF, 50-100 mg) are placed in a mortar and ground for 30-90 min; 5-10 ml of N-methylpyrrolidone (NMP) is added, and grinding is continued for 60-120 min to obtain a positive electrode slurry.

[0081] In an embodiment of the present invention, the preparation of the negative electrode slurry includes: uniformly stirring a negatively charged functional material with N-methylpyrrolidone to obtain a negative electrode slurry.

[0082] In some embodiments, 10-50 ml of AgCl slurry is taken; the AgCl slurry is mixed with 10-30 ml of NMP for 1-2 h to obtain a negative electrode slurry.

[0083] In operation S3, the first inert conductive metal layer and the second inert conductive metal layer are respectively bonded to the substrate 1, and the positive electrode paste and the negative electrode paste are respectively drop-coated onto the first inert conductive metal layer and the second inert conductive metal layer to form the positive electrode 2 and the negative electrode 3 on the substrate 1.

[0084] It should be noted that the positive electrode paste and the negative electrode paste can be first drop-coated onto the first inert conductive metal layer and the second inert conductive metal layer, respectively, and then the first inert conductive metal layer and the second inert conductive metal layer can be bonded onto the substrate 1.

[0085] In some embodiments, a positive electrode paste is added to a dispensing machine and uniformly dripped onto a first inert conductive metal layer to form a positive electrode 2.

[0086] In some embodiments, the negative electrode slurry is added to a dispensing machine and uniformly dripped onto the second inert conductive metal layer to form the negative electrode 3; wherein, there is a gap between the positive electrode 2 and the negative electrode 3, the width of which is 1~2mm, so as to electrically insulate the positive electrode 2 and the negative electrode 3.

[0087] In operation S4, the solid electrolyte slurry is drop-coated onto the positive electrode 2 and the negative electrode 3 respectively, and then dried to obtain solid electrolyte 4, wherein solid electrolyte 4 is connected to the positive electrode 2 and the negative electrode 3 respectively.

[0088] In embodiments of the present invention, the drying temperature is 40°C to 60°C, for example, 40°C, 50°C, or 60°C, but is not limited to the values ​​listed. The drying time is 10 to 30 minutes, for example, 10 minutes, 20 minutes, or 30 minutes, but is not limited to the values ​​listed.

[0089] Figure 2 This is a schematic diagram of the structure of a wireless moisture monitoring device for pharmaceuticals provided in an embodiment of the present invention.

[0090] According to an exemplary embodiment of the present invention, the present invention provides a wireless moisture monitoring device for pharmaceuticals, with reference to... Figure 2 As shown, it includes:

[0091] A container suitable for holding the medicine to be tested;

[0092] A heating platform, on which the container is placed, the heating platform being suitable for heating the drug to be tested;

[0093] The humidity gating device described above, placed inside the container, is suitable for outputting an electrical signal based on the humidity inside the container;

[0094] External circuit wires are respectively connected to the positive and negative electrodes of the humidity gate device, and are suitable for transmitting the electrical signal output by the humidity gate device to the electrical signal receiving device.

[0095] The electrical signal receiving device includes a wireless Bluetooth module, which is suitable for transmitting the electrical signal to a mobile device.

[0096] In some embodiments, the electrical signal receiving device includes, but is not limited to, the UNI-T UT60BT handheld Bluetooth digital multimeter with a wireless Bluetooth module and the WOO B35T+ high-precision digital display multimeter.

[0097] In some embodiments, the mobile device includes, but is not limited to, a mobile phone and an iPad.

[0098] In some embodiments, the heating temperature is, for example, 60°C. The lower heating temperature will not damage the drug structure, and the moisture content of the drug can be monitored in real time while ensuring the quality of the drug.

[0099] In an embodiment of the present invention, since drugs with different water contents will have different humidity levels inside the drug under heating conditions, the humidity gating device placed inside the container will capture different humidity signals and convert them into different electrical signals. After receiving the electrical signals, the electrical signal receiving device will upload the electrical signal data to the mobile device via a wireless Bluetooth module. Staff can observe the electrical signals in real time through the mobile device, thereby realizing real-time monitoring of humidity signals.

[0100] According to embodiments of the present invention, the drug moisture wireless monitoring device based on a humidity gating device combines a humidity gating device with ultra-high sensitivity, ultra-high stability and low manufacturing cost with an external detection device to achieve accurate monitoring of drug moisture content. This solves the technical problems of cumbersome monitoring operation, monitoring delay, and high monitoring cost, and has a very broad application prospect in the fields of medicine and health.

[0101] According to an embodiment of the present invention, the humidity-gated device does not require an external power source to provide additional energy, and can achieve self-driving functionality. Specifically, a potential difference exists between the positive and negative electrodes, which can provide energy to the device.

[0102] The following exemplifies the design of a humidity-gated device and its manufacturing method, as well as a wireless moisture monitoring device for pharmaceuticals. It should be noted that this exemplification is merely a specific embodiment of the present invention and does not limit the scope of protection of the present invention.

[0103] Example 1

[0104] A proton-gated device based on hydrophilic site modulation technology (i.e., the humidity-gated device of this invention) uses AgCl slurry as the negative electrode, aminated carbon nanotubes as the positive electrode, and Na+ as the solid electrolyte. + It is a mixture of HOF-BTB and PVA after domain restriction.

[0105] (1) Preparation of hydrogen-bonded organic framework HOF-BTB.

[0106] Specifically, BTB (43.84 mg) was dissolved in DMF (7.5 mL), and a clear solution was obtained by sonication for 10 minutes. Next, 9 mol of water was added to the solution. After stirring at room temperature for 8 h, a homogeneous colloidal suspension of HOF-BTB nanosheets was obtained. The suspension was washed with another 9 mol of water, filtered through a 0.45 μm aqueous membrane, and finally the filtrate was dissolved in water to form a 1.2 mg / mL HOF-BTB suspension.

[0107] (2) Preparation of NaCl-based HOF-BTB.

[0108] Specifically, 5 ml of a 1.2 mg / ml HOF-BTB suspension was placed in a beaker, and then a 2 mol / L NaCl solution was prepared. 200 μL of the prepared NaCl solution was added to the HOF-BTB suspension and mixed thoroughly for 1 hour, successfully preparing NaCl solution. + HOF-BTB with limited domain.

[0109] (3) Preparation of solid electrolyte.

[0110] Specifically, take 5ml of Na + The HOF-BTB suspension was confined, and then 1 ml of 1% PVA solution was taken. The two solutions were thoroughly mixed and stirred for 1 hour.

[0111] (4) Preparation of aminated carbon nanotube positive electrode slurry.

[0112] Specifically, aminated carbon nanotubes (70 mg) and polyvinylidene fluoride (PVDF) (30 mg) were placed in a mortar and ground for 60 min. 5 ml of NMP was added, and grinding continued for another 60 min.

[0113] (5) Preparation of AgCl negative electrode slurry.

[0114] Specifically, take 20 ml of AgCl slurry. Mix the AgCl slurry with 10 ml of NMP uniformly for 1 h.

[0115] (6) Device assembly.

[0116] Specifically, the above-mentioned aminated carbon nanotube positive electrode slurry and AgCl negative electrode slurry were drop-coated onto the surfaces of the first inert conductive metal layer (titanium sheet) and the second inert conductive metal layer (titanium sheet) of the substrate, respectively. Then, the solution used to prepare the solid electrolyte was drop-coated above the positive and negative electrodes, and dried at 60°C for 20 min to obtain a humidity-gated device.

[0117] Figure 3 This is a scanning electron microscope image of the positive electrode material provided in Embodiment 1 of the present invention.

[0118] Figure 4 This is a scanning electron microscope image of the negative electrode material provided in Embodiment 1 of the present invention.

[0119] refer to Figure 3 , Figure 4 As shown, both the prepared positive electrode material and the negative electrode material have a uniform and stable surface structure.

[0120] Figure 5The response / recovery curve of the humidity gating device provided in Embodiment 1 of the present invention is a single-time response curve.

[0121] refer to Figure 5 As shown, the humidity-gated device achieves 5 responses / recoveries within 200s, indicating that the device has an extremely high response / recovery speed.

[0122] Figure 6 The response / recovery curve of the humidity gating device provided in Embodiment 1 of the present invention after 200 cycles.

[0123] refer to Figure 6 As shown, the humidity-gated device showed no significant performance degradation after 200 cycles, proving its ultra-high stability.

[0124] (7) Method for identifying the moisture content of pharmaceutical products.

[0125] Specifically, a humidity-gated device is placed inside a medicine bottle to identify medicines with different moisture levels. 5 g of NaCl (acting as the medicine) is added to medicine bottles of the same volume, and different amounts of water (0.015-1 ml) are added to each bottle. A humidity-gated device is then placed inside each bottle. At 60°C, the humidity-gated device detects different current signals, which allow for precise monitoring of the medicine's moisture content.

[0126] Figure 7 The current curves for different drug moisture content identification by the wireless drug moisture monitoring device provided in Embodiment 1 of the present invention are shown. The horizontal axis represents the moisture content, and the vertical axis represents the current signals output by the positive and negative electrodes.

[0127] refer to Figure 7 As shown, when the moisture content in the drug increases, the current output signal of the humidity gating device increases accordingly, thus verifying that the device has the ability to accurately monitor the moisture content of the drug.

[0128] Example 2

[0129] A proton-gated device (i.e., a humidity-gated device) based on hydrophilic site modulation technology uses carboxylated carbon nanotubes as the negative electrode, amino-based graphene as the positive electrode, and Na+ as the solid electrolyte. + It is a mixture of HOF-H4TCPB and PVA after domain restriction.

[0130] (1) Preparation of hydrogen-bonded organic framework HOF-H4TCPB.

[0131] Specifically, H4TCPB (55.8 mg) was dissolved in DMF (7.5 mL), and a clear solution was obtained by sonication for 10 minutes. Next, 9 mol of water was added to the solution. After stirring at room temperature for 8 h, a homogeneous colloidal suspension of HOF-H4TCPB nanosheets was obtained. The suspension was washed again with 9 mol of water, filtered through a 0.45 μm aqueous membrane, and finally the filtrate was dissolved in water to form a 1.2 mg / mL HOF-BTB suspension.

[0132] (2) Preparation of NaCl-based HOF-H4TCPB.

[0133] Specifically, 5 ml of a 1.2 mg / ml HOF-H4TCPB suspension was placed in a beaker. Then, a 2 mol / L NaCl solution was prepared. 200 μL of the prepared NaCl solution was added to the HOF-H4TCPB suspension and mixed thoroughly for 1 h, successfully preparing NaCl solution. + HOF-BTB with limited domain.

[0134] (3) Preparation of solid electrolyte.

[0135] Specifically, take 5 ml of HOF-H4TCPB suspension based on hydrophilic site regulation technology, then take 1 ml of 1% PVA solution, mix the two solutions thoroughly and stir for 1 hour to obtain a solid electrolyte slurry.

[0136] (4) Preparation of amino-based graphene cathode material.

[0137] Specifically, amino-based graphene (70 mg) and polyvinylidene fluoride (PVDF) (30 mg) were ground in a mortar for 60 min. 5 ml of NMP was added, and grinding continued for another 60 min to obtain the positive electrode slurry.

[0138] (5) Preparation of carboxylated carbon nanotube anode materials.

[0139] Specifically, carboxylated graphene (70 mg) and polyvinylidene fluoride (PVDF) (30 mg) were placed in a mortar and ground for 60 min. 5 ml of NMP was added, and grinding was continued for another 60 min to obtain the negative electrode slurry.

[0140] (6) Device assembly.

[0141] Specifically, the above-mentioned aminated graphene positive electrode slurry and carboxylated carbon nanotube negative electrode slurry were drop-coated onto the surfaces of the first and second inert conductive metal layers (titanium sheets) of an insulating substrate. Then, a solid electrolyte slurry was drop-coated above the positive and negative electrodes, and dried at 60°C for 20 minutes to obtain a humidity-gated device. Subsequently, the humidity-gated device was placed inside a medicine bottle to identify medicines with different moisture levels.

[0142] Figure 8 The response / recovery curve of the humidity gating device provided in Embodiment 2 of the present invention is a single-time response curve.

[0143] refer to Figure 8 As shown, the humidity-gated device achieves 5 responses / recoveries within 100 seconds, indicating that the device has a high response / recovery speed.

[0144] Example 3

[0145] The humidity-gated device was fabricated using the same method as in Example 1, except that the amount of 2 mol / L NaCl solution used in the preparation of the NaCl-based HOF-BTB was 0. The response / recovery speed and on-off ratio of the humidity-gated device prepared in Example 3 are shown in the following test results. Figure 10 As shown.

[0146] Example 4

[0147] The humidity-gated device was fabricated using the same method as in Example 1, except that 1 μL of a 2 mol / L NaCl solution was used in the preparation of the NaCl-based HOF-BTB. The response / recovery speed and on / off ratio test results of the humidity-gated device prepared in Example 4 are as follows: Figure 10 As shown.

[0148] Example 5

[0149] The humidity-gated device was fabricated using the same method as in Example 1, except that 3 μL of a 2 mol / L NaCl solution was used in the preparation of the NaCl-based HOF-BTB. The response / recovery speed and on / off ratio test results of the humidity-gated device prepared in Example 5 are as follows: Figure 10 As shown.

[0150] Example 6

[0151] The humidity-gated device was fabricated using the same method as in Example 1, except that 5 μL of a 2 mol / L NaCl solution was used in the preparation of the NaCl-based HOF-BTB. The response / recovery speed and on / off ratio test results of the humidity-gated device prepared in Example 6 are as follows: Figure 10 As shown.

[0152] Example 7

[0153] The humidity-gated device was fabricated using the same method as in Example 1, except that 7 μL of a 2 mol / L NaCl solution was used in the preparation of the NaCl-based HOF-BTB. The response / recovery speed and on / off ratio test results of the humidity-gated device prepared in Example 7 are as follows: Figure 10 As shown.

[0154] Example 8

[0155] The humidity-gated device was fabricated using the same method as in Example 1, except that 10 μL of a 2 mol / L NaCl solution was used in the preparation of the NaCl-based HOF-BTB. The response / recovery speed and on / off ratio test results of the humidity-gated device prepared in Example 8 are as follows: Figure 10 As shown.

[0156] Example 9

[0157] The humidity-gated device was fabricated using the same method as in Example 1, except that 20 μL of a 2 mol / L NaCl solution was used in the preparation of the NaCl-based HOF-BTB. The response / recovery speed and on / off ratio test results of the humidity-gated device prepared in Example 9 are as follows: Figure 10 As shown.

[0158] Example 10

[0159] The humidity-gated device was fabricated using the same method as in Example 1, except that 50 μL of a 2 mol / L NaCl solution was used in the preparation of the NaCl-based HOF-BTB. The response / recovery speed and on / off ratio test results of the humidity-gated device prepared in Example 10 are as follows: Figure 10 As shown.

[0160] Example 11

[0161] The humidity-gated device was fabricated using the same method as in Example 1, except that 100 μL of a 2 mol / L NaCl solution was used in the preparation of the NaCl-based HOF-BTB. The response / recovery speed and on / off ratio test results of the humidity-gated device prepared in Example 11 are as follows: Figure 10 As shown.

[0162] Example 12

[0163] The humidity-gated device was fabricated using the same method as in Example 1, except that 500 μL of a 2 mol / L NaCl solution was used in the preparation of the NaCl-based HOF-BTB. The response / recovery speed and on / off ratio test results of the humidity-gated device prepared in Example 12 are as follows: Figure 10 As shown.

[0164] Example 13

[0165] The humidity-gated device was fabricated using the same method as in Example 1, except that 1000 μL of a 2 mol / L NaCl solution was used in the preparation of the NaCl-based HOF-BTB. The response / recovery speed and on / off ratio test results of the humidity-gated device prepared in Example 13 are as follows: Figure 10 As shown.

[0166] Figure 9 Scanning electron microscope (SEM) images of HOF-BTB nanoribbon structures under different NaCl solution addition amounts provided in embodiments of the present invention.

[0167] Figure 10 This is a comparison chart of the response / recovery speed and on / off ratio of humidity gating devices prepared with different amounts of NaCl solution added according to embodiments of the present invention.

[0168] refer to Figure 9 As shown, with increasing NaCl concentration, obvious salt particles appeared on the surface of the HOF-BTB nanoribbons, while the nanoribbon structure remained intact. This indicates that the addition of NaCl does not damage the HOF nanoribbon structure.

[0169] refer to Figure 10As shown in Examples 1 and 3-13, adjusting the amount of NaCl solution can alter the response / recovery speed and on / off ratio of the humidity-gated device. According to Examples 3-11, devices with less than 200 μL of NaCl added exhibit poor response / recovery and a low on / off ratio. This is because the low NaCl content results in low water absorption efficiency of the solid electrolyte. According to Examples 12-13, devices with more than 200 μL of NaCl show strong response / recovery, but the on / off ratio also decreases. This is because excessively high NaCl content leads to lower dehydration efficiency of the solid electrolyte, increased off-state current, and consequently, a lower on / off ratio.

[0170] By controlling the molar ratio of HOF-BTB to NaCl solution to (1~5):(0.02~0.1), excellent response / recovery speed and on / off ratio can be obtained, with the response / recovery speed reaching over 1000 ns / A and the on / off ratio reaching over 6000.

[0171] Example 14

[0172] The humidity-gated device was fabricated using the same method as in Example 1, except that the amount of 1% PVA solution used in the preparation of the solid electrolyte was 0.1 ml. The response / recovery speed and on / off ratio test results of the humidity-gated device prepared in Example 14 are as follows: Figure 12 As shown.

[0173] Example 15

[0174] The humidity-gated device was fabricated using the same method as in Example 1, except that the amount of 1% PVA solution used in the preparation of the solid electrolyte was 0.2 ml. The response / recovery speed and on / off ratio test results of the humidity-gated device prepared in Example 15 are as follows: Figure 12 As shown.

[0175] Example 16

[0176] The humidity-gated device was fabricated using the same method as in Example 1, except that the amount of 1% PVA solution used in the preparation of the solid electrolyte was 0.5 ml. The response / recovery speed and on / off ratio test results of the humidity-gated device prepared in Example 16 are as follows: Figure 12 As shown.

[0177] Example 17

[0178] The humidity-gated device was fabricated using the same method as in Example 1, except that 2 ml of a 1% PVA solution was used in the preparation of the solid electrolyte. The response / recovery speed and on / off ratio test results of the humidity-gated device prepared in Example 17 are as follows: Figure 12 As shown.

[0179] Example 18

[0180] The humidity-gated device was fabricated using the same method as in Example 1, except that 3 ml of a 1% PVA solution was used in the preparation of the solid electrolyte. The response / recovery speed and on / off ratio test results of the humidity-gated device prepared in Example 18 are as follows: Figure 12 As shown.

[0181] Example 19

[0182] The humidity-gated device was fabricated using the same method as in Example 1, except that 4 ml of a 1% PVA solution was used in the preparation of the solid electrolyte. The response / recovery speed and on / off ratio test results of the humidity-gated device prepared in Example 19 are as follows: Figure 12 As shown.

[0183] Figure 11 Scanning electron microscope (SEM) images of HOF-BTB nanoribbon structures under different PVA solution addition amounts provided by this invention.

[0184] Figure 12 A comparison chart of the response / recovery speed and on / off ratio of humidity gating devices prepared with different amounts of PVA solution provided by the present invention.

[0185] refer to Figure 11 As shown, when the amount of PVA added is greater than 1 ml, it is obvious that the pores of the HOF-BTB nanoribbon structure are blocked.

[0186] refer to Figure 12 As shown, devices with less than 1 ml of PVA added exhibit poor response / recovery and a low on / off ratio. This is due to the low PVA content, which leads to poor mechanical properties of the solid electrolyte. Devices with more than 1 ml of PVA added also show a decrease in response / recovery and on / off ratio. This is because the excessively high PVA content clogs the pores of the solid electrolyte membrane, reducing ion mobility.

[0187] By controlling the molar ratio of HOF-BTB to PVA to (1~5):(0.01~0.1), excellent response / recovery speed and on / off ratio can be obtained, with the response / recovery speed reaching more than 1000ns / A and the on / off ratio reaching more than 6000.

[0188] The specific embodiments described above further illustrate the purpose, technical solution, and beneficial effects of the present invention. It should be understood that the above descriptions are merely specific embodiments of the present invention and are not intended to limit the present invention. Any modifications, equivalent substitutions, improvements, etc., made within the spirit and principles of the present invention should be included within the protection scope of the present invention.

Claims

1. A humidity-gated device, characterized in that, include: Base (1); The positive electrode (2) and the negative electrode (3) are located on the same surface of the substrate (1), and there is a gap between the positive electrode (2) and the negative electrode (3); A solid electrolyte (4) is located at least partially within the void, and the solid electrolyte (4) is connected to the positive electrode (2) and the negative electrode (3) respectively. The ionic conductivity of the solid electrolyte (4) changes in response to the change in humidity of the test environment. In response to the change in the ionic conductivity of the solid electrolyte (4) affected by humidity, the electrical signals output by the positive electrode and the negative electrode change, and the electrical signals are used to characterize the humidity of the environment to be measured.

2. The humidity gating device according to claim 1, characterized in that, The substrate is made of a flexible insulating material; Preferably, the flexible insulating material includes at least one of polyethylene terephthalate plastic sheet and polyimide plastic sheet.

3. The humidity gating device according to claim 1, characterized in that, Solid electrolytes contain hydrogen-bonded organic frameworks, polymers, and metal ions confined by the hydrogen-bonded organic frameworks.

4. The humidity gating device according to claim 3, characterized in that, The monomers that form the hydrogen-bonded organic framework include at least one of 1,3,5-tris(4-carboxyphenyl)benzene, 1,2,4,5-tetra(4-carboxyphenyl)benzene, and N,N,N',N'-tetra(p-aminophenyl)p-phenylenediamine.

5. The humidity gating device according to claim 3, characterized in that, The polymer includes at least one of bacterial cellulose and polyvinyl alcohol.

6. The humidity gating device according to claim 3, characterized in that, The metal ions confined by the hydrogen-bonded organic framework originate from an ionic solution, which includes at least one of NaCl solution and KCl solution; Preferably, the concentration of the ionic solution is 1~5 mol / L; Preferably, the molar ratio of the hydrogen-bonded organic framework, the polymer, and the ionic solution is (1~5):(0.01~0.1):(0.02~0.1).

7. The humidity gating device according to claim 1, characterized in that, The positive electrode comprises a positively charged functional material loaded on a first inert conductive metal layer, and the first inert conductive metal layer is loaded on the substrate; Preferably, the positively charged functional material includes at least one of aminated carbon nanotubes and aminated graphene; Preferably, the negative electrode comprises a negatively charged functional material loaded on a second inert conductive metal layer, and the second inert conductive metal layer is loaded on the substrate; Preferably, the negatively charged functional material includes at least one of carboxylated carbon nanotubes and AgCl slurry.

8. A method for manufacturing a humidity-gated device as described in any one of claims 1 to 7, characterized in that, include: Preparation of solid electrolyte slurry; Positive electrode slurry and negative electrode slurry were prepared separately; A first inert conductive metal layer and a second inert conductive metal layer are respectively bonded to a substrate (1). A positive electrode paste and a negative electrode paste are respectively drop-coated onto the first inert conductive metal layer and the second inert conductive metal layer to form a positive electrode (2) and a negative electrode (3) on the substrate (1); and Solid electrolyte slurry was dripped onto the positive electrode (2) and the negative electrode (3) respectively, and then dried to obtain solid electrolyte (4), wherein the solid electrolyte (4) was connected to the positive electrode (2) and the negative electrode (3) respectively.

9. The manufacturing method according to claim 8, characterized in that, The preparation of solid electrolyte slurry includes: An ion-confined hydrogen-bonded organic framework suspension was prepared by mixing an ionic solution with a hydrogen-bonded organic framework suspension and stirring thoroughly. A solid electrolyte slurry is obtained by mixing and stirring an ion-confined hydrogen-bonded organic framework suspension with a polymer. Preferably, the preparation of the hydrogen-bonded organic framework suspension includes: Hydrogen-bonded organic framework monomers were dissolved in N,N-dimethylformamide and a clear solution was obtained by sonication. Water was added to the clarified solution, and the mixture was stirred at room temperature to obtain a uniform colloidal suspension of hydrogen-bonded organic frameworks. Water was added to the homogeneous colloidal suspension of the hydrogen-bonded organic framework for washing, and the mixture was filtered using a 0.45 μm aqueous membrane. Finally, the filtrate was dissolved in water to form a hydrogen-bonded organic framework suspension. Preferably, the preparation of the positive electrode slurry includes: The positively charged functional material and polyvinylidene fluoride were mixed and ground to obtain a first mixture; N-methylpyrrolidone was added to the first mixture and ground to obtain a positive electrode slurry. Preferably, the preparation of the negative electrode slurry includes: The negatively charged functional material is uniformly stirred with N-methylpyrrolidone to obtain a negative electrode slurry.

10. A wireless moisture monitoring device for pharmaceuticals, characterized in that, include: A container suitable for holding the medicine to be tested; A heating platform, on which the container is placed, the heating platform being suitable for heating the drug to be tested; The humidity gating device as described in any one of claims 1 to 7, placed inside the container, is adapted to output an electrical signal based on the humidity inside the container; External circuit wires are respectively connected to the positive and negative electrodes of the humidity gate device, and are suitable for transmitting the electrical signal output by the humidity gate device to the electrical signal receiving device. The electrical signal receiving device includes a wireless Bluetooth module, which is suitable for transmitting the electrical signal to a mobile device.

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