Fiber type zinc ion power supply temperature sensor and preparation method and application thereof

Abstract

The invention discloses a fiber type zinc ion power supply temperature sensor and a preparation method and application thereof, and relates to the field of flexible electronic devices. When the fiber type zinc ion power supply temperature sensor is prepared, aramid fiber and polyvinyl alcohol are dissolved in a dimethylacetamide / lithium chloride solvent, reduced graphene oxide and manganese dioxide are doped, and the fiber type temperature sensor is prepared through wet spinning and Ecoflex / boron nitride coating packaging. A polyacrylamide electrolyte solution containing zinc sulfate and manganese sulfate is injected into the space between the carbon fiber positive electrode coated with the carbon black, manganese dioxide and polyvinylidene fluoride slurry and the zinc wire negative electrode; after photopolymerization, Ecoflex packaging is performed to prepare the fiber type zinc ion battery; and integrating the fiber type temperature sensor and the fiber type zinc ion battery to obtain the fiber type zinc ion power supply temperature sensor. The prepared temperature sensor can continuously monitor the body temperature of a human body in the movement process in real time, and early-stage heating detection is achieved by capturing fine abnormal temperature fluctuation.

Description

Technical Field

[0001] This invention relates to the field of flexible electronic device technology, specifically to a fiber-type zinc ion powered temperature sensor, its preparation method, and its application. Background Technology

[0002] Flexible sensors can detect physical, chemical, and biological information about the human body and environment, and have enormous application potential in fields such as health management and humanoid robots. Body temperature, as a critical vital sign, is essential for maintaining normal life activities; excessively high or low body temperatures can seriously harm health. Furthermore, various diseases can disrupt the body's normal thermoregulation mechanisms, leading to abnormal body temperatures. However, most reported temperature sensors are based on solid polymer film substrates, which hinder the perspiration process during normal physiological activities, inevitably leading to skin redness and inflammation. This problem is even more pronounced in body temperature monitoring during exercise and fever, due to the higher body temperature and frequent sweating. On the other hand, continuous long-term temperature sensing and monitoring heavily relies on high-performance power supplies, but traditional rigid batteries have limitations such as large size and poor flexibility, making them unsuitable for wearable applications. Therefore, there is an urgent need to develop a fiber-type flexible battery-powered temperature sensor to meet the stringent requirements of portable, long-term wearable body temperature detection. This is crucial for promoting the practical application of wearable health monitoring technology and improving the continuity and comfort of human physiological signal monitoring. Summary of the Invention

[0003] The purpose of this invention is to provide a fiber-type zinc ion powered temperature sensor, its preparation method, and its application, so as to solve the problems existing in the prior art.

[0004] To solve the above-mentioned technical problems, the present invention provides the following technical solution: A fiber-type zinc ion powered temperature sensor is fabricated by integrating a fiber-type temperature sensor with a fiber-type zinc ion battery.

[0005] As an optimization, the fiber-type temperature sensor is made by wet spinning and encapsulating a thermosensitive mixture with an Ecoflex / boron nitride coating.

[0006] As an optimization, the thermosensitive mixture is prepared by dissolving aramid and polyvinyl alcohol in a dimethylacetamide / lithium chloride mixed solvent and then incorporating reduced graphene oxide and manganese dioxide.

[0007] As an optimization, the fiber-type zinc-ion battery is prepared by injecting a polyacrylamide electrolyte solution containing zinc sulfate and manganese sulfate between a carbon fiber positive electrode and a zinc wire negative electrode, followed by ultraviolet light polymerization and Ecoflex encapsulation.

[0008] As an optimization, the carbon fiber cathode is prepared by coating carbon fiber with a mixed slurry of carbon black, manganese dioxide, and polyvinylidene fluoride.

[0009] A method for fabricating a fiber-type zinc ion powered temperature sensor includes the following fabrication steps: (1) Mix dimethylacetamide and lithium chloride solution at a mass ratio of 1:2~6, and stir at 200~300 r / min for 10~30 min at 25~30℃ to obtain a mixed solvent; mix aramid and polyvinyl alcohol at a mass ratio of 1:0.1~0.4, and add them to the mixed solvent at a solid-liquid ratio of 1:10~14, and stir at 200~300 r / min for 4 h at 85~105℃ to obtain a polymer solution; mix reduced graphene oxide and manganese dioxide at a mass ratio of 3~5:1, and add them to the polymer solution at a solid-liquid ratio of 1:14~15 and continue stirring for 1 h to obtain a thermosensitive mixture; transfer the thermosensitive mixture to... The fibers were transferred to a syringe and injected into a water bath at a rate of 3-7 mL / h using a wet spinning machine. The resulting fibers were then removed, washed 3-5 times with deionized water, and dried at 50-70℃ for 20-40 min to obtain Aramid / PVA / rGO / MnO2 fibers. Ecoflex and boron nitride were mixed evenly at a mass ratio of 1:0.1-0.4 to obtain a coating mixture. The Aramid / PVA / rGO / MnO2 fibers were immersed in the coating mixture for 3-7 min, pulled up, and allowed to stand at room temperature for 20-40 min to level. They were then dried at 25-30℃ for 1-3 h to obtain a fiber-type temperature sensor. (2) Carbon black, manganese dioxide, polyvinylidene fluoride and N-methylpyrrolidone solvent are mixed evenly in a mass ratio of 1:(0.15~0.45):(0.05~0.2):(140~160), and ground for 10~30 min to obtain a mixed slurry; conductive carbon fibers are immersed in the mixed slurry for 3~7 min, pulled up and dried at 70~90℃ for 0.5~1.5 h to obtain manganese dioxide modified carbon fiber positive electrode; acrylamide, ammonium persulfate, N,N-methylenebisacrylamide, tetramethylethylenediamine and deionized water are mixed evenly in a mass ratio of 1:(0.005~0.007):(0.005~0.007):(0.006~0.008):(4~6). Mix 1.75-2.25 mol / L zinc sulfate and 0.1-0.3 mol / L manganese sulfate, and stir at 200-300 r / min for 20-40 min at 25-30℃ to obtain a polyacrylamide electrolyte solution. Fix manganese dioxide-modified carbon fiber positive electrode and zinc wire negative electrode parallel to both sides of the inner wall of a polyvinyl chloride hose, inject the polyacrylamide electrolyte solution until the electrodes are submerged, and irradiate under 365 nm ultraviolet light for 1-5 min to obtain a polyacrylamide gel electrolyte. Peel the polyacrylamide gel electrolyte from the polyvinyl chloride hose mold, immerse it in Ecoflex for 3-7 min, pull it out, and dry it at 25-30℃ for 1.5-2.5 h to obtain a fiber-type zinc-ion battery. (3) The fiber-type temperature sensor is connected to the printed circuit board through wires to form the basic link for signal transmission and processing; the fiber-type zinc-ion battery is connected to the DC-DC converter to provide a constant voltage to the sensor and then connected to the printed circuit board to obtain the fiber-type zinc-ion powered temperature sensor.

[0010] As an optimization, the aramid in step (1) is 1313 short-cut fiber, manufactured by Hubei Tengdi New Materials Co., Ltd.; the polyvinyl alcohol is type 124, manufactured by Shanghai Yuanye Biotechnology Co., Ltd.; the reduced graphene oxide is multilayer reduced graphene oxide, manufactured by Suzhou Carbon Peak Graphene Technology Co., Ltd.; the Ecoflex is type 00-30, purchased from Smooth On, USA; the boron nitride size is 1μm, manufactured by Zhongbei Nanopowder Technology Co., Ltd.

[0011] As an optimization, the syringe in step (1) is a 10ml syringe with a needle diameter of 1.8mm.

[0012] As an optimization, the carbon black in step (2) is Super P Li carbon black, manufactured by Guangdong Zhuguang New Energy Technology Co., Ltd.; the polyvinylidene fluoride has a molecular weight of 90,000, manufactured by Guangdong Zhuguang New Energy Technology Co., Ltd.; the conductive carbon fiber is model T300-1K, manufactured by Youbaite New Material Technology Co., Ltd.; and the zinc wire has a size of 0.5mm, purchased from Hebei Guantai Metal Materials Co., Ltd.

[0013] Compared with the prior art, the beneficial effects achieved by the present invention are: In the preparation of the fiber-type zinc-ion powered temperature sensor, this invention involves dissolving aramid and polyvinyl alcohol in a dimethylacetamide / lithium chloride solvent, incorporating reduced graphene oxide and manganese dioxide, and then wet-spinning and encapsulating with an Ecoflex / boron nitride coating to form a fiber-type temperature sensor. A polyacrylamide electrolyte solution containing zinc sulfate and manganese sulfate is injected between a carbon fiber positive electrode coated with carbon black, manganese dioxide, and polyvinylidene fluoride slurry and a zinc wire negative electrode, followed by photopolymerization and encapsulation with Ecoflex to obtain a fiber-type zinc-ion battery. The fiber-type temperature sensor and the fiber-type zinc-ion battery are then integrated to obtain a fiber-type zinc-ion powered temperature sensor.

[0014] First, a polymer substrate with a near-zero coefficient of thermal expansion was constructed by optimizing the component ratio of aramid and polyvinyl alcohol. Simultaneously, a highly conductive network was built using reduced graphene oxide and manganese dioxide. Aramid, polyvinyl alcohol, reduced graphene oxide, and manganese dioxide were dissolved in a mixed solution of dimethylacetamide and lithium chloride, and then spun in a water bath using wet spinning technology to obtain highly conductive fibers. Subsequently, a hybrid encapsulation layer of Ecoflex and boron nitride was coated onto the fiber surface to obtain the final temperature sensor. Boron nitride accelerates heat conduction, enabling rapid sensor response; the Ecoflex layer effectively prevents internal moisture evaporation and external moisture intrusion, significantly improving the sensor's flexibility, stability, and environmental tolerance.

[0015] Secondly, the fiber-type zinc-ion battery consists of a manganese dioxide-modified carbon fiber positive electrode, a zinc wire negative electrode, a polyacrylamide gel polymer electrolyte, and an Ecoflex encapsulation layer. Its fabrication employs an integrated process: the manganese dioxide-modified carbon fiber positive electrode and the zinc wire negative electrode are arranged parallel to each other on both sides of the inner wall of a flexible tube, a polyacrylamide electrolyte solution is cast, and ultraviolet light polymerization is performed. Subsequently, the tube is peeled off and encapsulated with Ecoflex to obtain the fiber-type zinc-ion battery. Ecoflex encapsulation not only effectively prevents moisture evaporation from the gel electrolyte but also avoids separation of the positive and negative electrodes from the electrolyte, ensuring the battery's excellent rechargeable and dischargeable performance and long-term stability. The fabricated fiber-type temperature sensor can be used for object material identification. When integrated with the fiber-type zinc-ion battery and embedded in clothing, it can achieve precise medical and health monitoring and early disease diagnosis based on real-time body temperature data. Attached Figure Description

[0016] Figure 1 This is a schematic diagram illustrating the fabrication and structure of the fiber-type zinc ion powered temperature sensor described in this invention. Figure 2 This is a schematic diagram illustrating the high reproducibility principle of the fiber-type temperature sensor described in this invention. Figure 3 This is an electron microscope image of the fiber-type temperature sensor in Embodiment 1 of the present invention; Figure 4 This is an electron microscope image of the fiber-type zinc-ion battery in Embodiment 1 of the present invention; Figure 5 middle, Figure 5 a is a test graph showing the high reproducibility of a fiber-type temperature sensor; Figure 5 b is a graph showing the sensor's response to a minute temperature change of 0.1°C; Figure 6 middle, Figure 6 a is the open-circuit voltage test diagram of a fiber-type zinc-ion battery; Figure 6 b is the CV curve test graph of the fiber-type zinc-ion battery; Figure 6 c is the rate performance test graph of the fiber-type zinc-ion battery; Figure 7 This is a graph showing the relative resistance response of the fiber-type temperature sensor described in this invention when it comes into contact with a standard cube made of six different materials. Figure 8 The fiber-type zinc ion-powered temperature sensor described in this invention monitors changes in human body temperature; wherein, Figure 8 a is a photograph of the neck temperature detected by the sensor, verified by infrared thermal imaging; Figure 8 b is a graph showing body temperature monitoring of a person under different activity states: resting, walking, and running. Figure 8 c is a comparison chart of fiber-type temperature sensors and commercial sensors; Figure 8 d. Schematic diagram of a wearable sensing system for fever detection; Figure 8 e represents the resistance curves corresponding to the sensor's monitoring of normal body temperature and various fever conditions; Figure 8 f is the output voltage curve of a wearable system powered by a fiber-type zinc-ion battery; Explanation of reference numerals in the attached figures: 1-Fiber-type temperature sensor, 2-Fiber-type zinc-ion battery, 3-Wet spinning machine, 4-Water bath, 5-Ecoflex / boron nitride mixture, 6-Thermistor fiber, 7-Ecoflex / boron nitride encapsulation layer, 8-Negative electrode, 9-Positive electrode, 10-Ecoflex encapsulation layer, 11-Polyacrylamide gel electrolyte. Detailed Implementation

[0017] The technical solutions of the present invention will be clearly and completely described below with reference to the embodiments of the present invention. Obviously, the described embodiments are only some embodiments of the present invention, and not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those of ordinary skill in the art without creative effort are within the scope of protection of the present invention.

[0018] To more clearly illustrate the method provided by the present invention, the following embodiments will be described in detail.

[0019] Example 1: A method for fabricating a fiber-type zinc ion powered temperature sensor includes the following fabrication steps: (1) Mix dimethylacetamide and lithium chloride solution at a mass ratio of 1:4 and stir at 27°C and 250 r / min for 20 min to obtain a mixed solvent; mix aramid and polyvinyl alcohol at a mass ratio of 1:0.3 and add them to the mixed solvent at a solid-liquid ratio of 1:12, and stir at 95°C and 250 r / min for 4 h to obtain a polymer solution; mix reduced graphene oxide and manganese dioxide at a mass ratio of 4:1 and add them to the polymer solution at a solid-liquid ratio of 1:14~15 and continue stirring. After 1 hour, a thermosensitive mixture was obtained. The thermosensitive mixture was transferred to a syringe and injected into a water bath at a rate of 5 mL / h using a wet spinning machine. The resulting fibers were removed, washed four times with deionized water, and dried at 60°C for 30 min to obtain Aramid / PVA / rGO / MnO2 fibers. Ecoflex and boron nitride were mixed evenly at a mass ratio of 1:0.1 to obtain a coating mixture. The Aramid / PVA / rGO / MnO2 fibers were immersed in the coating mixture for 5 min, pulled up, and allowed to stand at room temperature for 30 min to level. They were then dried at 30°C for 2 h to obtain a fiber-type temperature sensor. (2) Carbon black, manganese dioxide, polyvinylidene fluoride and N-methylpyrrolidone solvent were mixed evenly in a mass ratio of 1:0.3:0.14:150 and ground for 20 min to obtain a mixed slurry; conductive carbon fibers were immersed in the mixed slurry for 5 min, pulled up and dried at 80℃ for 1 h to obtain manganese dioxide modified carbon fiber positive electrode; acrylamide, ammonium persulfate, N,N-methylenebisacrylamide, tetramethylethylenediamine and deionized water were mixed evenly in a mass ratio of 1:0.006:0.006:0.007:5, and 2 mol / L sulfur was added. Zinc sulfate and 0.2 mol / L manganese sulfate were stirred at 25°C and 250 r / min for 30 min to prepare a polyacrylamide electrolyte solution. Manganese dioxide-modified carbon fiber positive electrode and zinc wire negative electrode were fixed parallel to each other on both sides of the inner wall of the tubing. The polyacrylamide electrolyte solution was injected until the electrodes were submerged. Polymerization was initiated by irradiation under 365 nm ultraviolet light for 3 min to prepare a polyacrylamide gel electrolyte. The polyacrylamide gel electrolyte was peeled off the tubing mold, immersed in Ecoflex for 5 min, pulled out and dried at 30°C for 2 h to prepare a fiber-type zinc-ion battery. (3) The fiber-type temperature sensor is connected to the printed circuit board through wires to form the basic link for signal transmission and processing; the fiber-type zinc-ion battery is connected to the DC-DC converter to provide a constant voltage to the sensor and then connected to the printed circuit board to obtain the fiber-type zinc-ion powered temperature sensor.

[0020] Comparative Example 1: The only difference from Example 1 is step (1), in which the Ecoflex / boron nitride coating encapsulation step in step (1) is removed.

[0021] Comparative Example 2: The only difference from Example 1 is the difference in step (1). The phrase "mixing reduced graphene oxide and manganese dioxide at a mass ratio of 4:1 and then adding it to the polymer solution at a solid-liquid ratio of 1:14~15 and stirring for 1 hour to obtain a thermosensitive mixture" in step (1) is changed to "mixing reduced graphene oxide and manganese dioxide at a mass ratio of 3:1 and then adding it to the polymer solution at a solid-liquid ratio of 1:14~15 and stirring for 1 hour to obtain a thermosensitive mixture"; and the Ecoflex / boron nitride coating encapsulation step in step (1) is deleted.

[0022] Comparative Example 3: The only difference from Example 1 is the difference in step (1). The phrase "mixing reduced graphene oxide and manganese dioxide at a mass ratio of 4:1 and then adding it to the polymer solution at a solid-liquid ratio of 1:14~15 and stirring for 1 hour to obtain a thermosensitive mixture" in step (1) is changed to "mixing reduced graphene oxide and manganese dioxide at a mass ratio of 5:1 and then adding it to the polymer solution at a solid-liquid ratio of 1:14~15 and stirring for 1 hour to obtain a thermosensitive mixture"; and the Ecoflex / boron nitride coating encapsulation step in step (1) is deleted.

[0023] Comparative Example 4: A method for fabricating a fiber-type zinc ion powered temperature sensor includes the following fabrication steps: (1) Mix dimethylacetamide and lithium chloride solution at a mass ratio of 1:4 and stir at 27°C and 250 r / min for 20 min to obtain a mixed solvent; add aramid and mixed solvent at a solid-liquid ratio of 1:16 to the mixed solvent and stir at 95°C and 250 r / min for 4 h to obtain a polymer solution; mix reduced graphene oxide and manganese dioxide at a mass ratio of 4:1 and add to the polymer solution at a solid-liquid ratio of 1:14~15 and continue stirring for 1 h to obtain a thermosensitive mixture; transfer the thermosensitive mixture to a syringe and inject it into a water bath at a speed of 5 mL / h using a wet spinning machine; take out the obtained fiber, wash it 4 times with deionized water, and dry it at 60°C for 30 min to obtain an Aramid / rGO / MnO2 fiber type temperature sensor; (2) Carbon black, manganese dioxide, polyvinylidene fluoride and N-methylpyrrolidone solvent were mixed evenly in a mass ratio of 1:0.3:0.14:150 and ground for 20 min to obtain a mixed slurry; conductive carbon fibers were immersed in the mixed slurry for 5 min, pulled up and dried at 80℃ for 1 h to obtain manganese dioxide modified carbon fiber positive electrode; acrylamide, ammonium persulfate, N,N-methylenebisacrylamide, tetramethylethylenediamine and deionized water were mixed evenly in a mass ratio of 1:0.006:0.006:0.007:5, and 2 mol / L sulfur was added. Zinc sulfate and 0.2 mol / L manganese sulfate were stirred at 25°C and 250 r / min for 30 min to prepare a polyacrylamide electrolyte solution. Manganese dioxide-modified carbon fiber positive electrode and zinc wire negative electrode were fixed parallel to each other on both sides of the inner wall of the tubing. The polyacrylamide electrolyte solution was injected until the electrodes were submerged. Polymerization was initiated by irradiation under 365 nm ultraviolet light for 3 min to prepare a polyacrylamide gel electrolyte. The polyacrylamide gel electrolyte was peeled off the tubing mold, immersed in Ecoflex for 5 min, pulled out and dried at 30°C for 2 h to prepare a fiber-type zinc-ion battery. (3) The fiber-type temperature sensor is connected to the printed circuit board through wires to form the basic link for signal transmission and processing; the fiber-type zinc-ion battery is connected to the DC-DC converter to provide a constant voltage to the sensor and then connected to the printed circuit board to obtain the fiber-type zinc-ion powered temperature sensor.

[0024] Comparative Example 5: A method for fabricating a fiber-type zinc ion powered temperature sensor includes the following fabrication steps: (1) Mix dimethylacetamide and lithium chloride solution at a mass ratio of 1:4 and stir at 27°C and 250 r / min for 20 min to obtain a mixed solvent; add polyvinyl alcohol and mixed solvent at a solid-liquid ratio of 1:54 to the mixed solvent and stir at 95°C and 250 r / min for 4 h to obtain a polymer solution; mix reduced graphene oxide and manganese dioxide at a mass ratio of 4:1 and add them to the polymer solution at a solid-liquid ratio of 1:14~15 and continue stirring for 1 h to obtain a thermosensitive mixture; transfer the thermosensitive mixture to a syringe and inject it into a water bath at a speed of 5 mL / h through a wet spinning machine; take out the obtained fiber, wash it 4 times with deionized water, and dry it at 60°C for 30 min to obtain a PVA / rGO / MnO2 fiber type temperature sensor; (2) Carbon black, manganese dioxide, polyvinylidene fluoride and N-methylpyrrolidone solvent were mixed evenly in a mass ratio of 1:0.3:0.14:150 and ground for 20 min to obtain a mixed slurry; conductive carbon fibers were immersed in the mixed slurry for 5 min, pulled up and dried at 80℃ for 1 h to obtain manganese dioxide modified carbon fiber positive electrode; acrylamide, ammonium persulfate, N,N-methylenebisacrylamide, tetramethylethylenediamine and deionized water were mixed evenly in a mass ratio of 1:0.006:0.006:0.007:5, and 2 mol / L sulfur was added. Zinc sulfate and 0.2 mol / L manganese sulfate were stirred at 25°C and 250 r / min for 30 min to prepare a polyacrylamide electrolyte solution. Manganese dioxide-modified carbon fiber positive electrode and zinc wire negative electrode were fixed parallel to each other on both sides of the inner wall of the tubing. The polyacrylamide electrolyte solution was injected until the electrodes were submerged. Polymerization was initiated by irradiation under 365 nm ultraviolet light for 3 min to prepare a polyacrylamide gel electrolyte. The polyacrylamide gel electrolyte was peeled off the tubing mold, immersed in Ecoflex for 5 min, pulled out and dried at 30°C for 2 h to prepare a fiber-type zinc-ion battery. (3) The fiber-type temperature sensor is connected to the printed circuit board through wires to form the basic link for signal transmission and processing; the fiber-type zinc-ion battery is connected to the DC-DC converter to provide a constant voltage to the sensor and then connected to the printed circuit board to obtain the fiber-type zinc-ion powered temperature sensor.

[0025] Experimental Example 1: Sensitivity tests were performed on Example 1 and Comparative Examples 1-3.

[0026] Sensitivity testing method: The sensor was placed on a heating stage and connected to a digital source meter to collect temperature-resistance change curves. The effects of different reduced graphene oxide contents and whether or not there is encapsulation on the sensitivity of the prepared fiber-type temperature sensor were studied.

[0027] Sensitivity = ; The change in resistance, The initial resistance of the sensor is . The resistance at temperature t; The change in temperature The initial temperature, Let t be the temperature at temperature t.

[0028] The results are shown in Table 1.

[0029] Table 1

[0030] As shown in Table 1, the proportion of reduced graphene oxide (PBO) significantly affects the performance of the temperature sensor. With increasing PBO content, the sensor performance initially improves and then declines. This is because when the PBO content exceeds a certain threshold, the conductive filler agglomerates in the polymer substrate, disrupting the originally uniform conductive network structure and consequently reducing sensor sensitivity. This phenomenon can be attributed to the difficulty in uniformly dispersing excessive PBO in the substrate, easily forming localized dense regions that hinder effective electron transport paths. Furthermore, the use of the Ecoflex / boron nitride encapsulation layer has virtually no significant impact on sensor sensitivity; simultaneously, thanks to the inherently excellent thermal conductivity of boron nitride, this encapsulation layer significantly shortens the sensor's response and recovery times.

[0031] Experimental Example 2: Sensitivity and expansion coefficient tests were performed on Example 1 and Comparative Examples 4-5. The sensitivity test method is the same as in Experiment 1.

[0032] Expansion coefficient test method: Expansion curves were obtained using a thermal dilatometer. The sensor was subjected to cyclic heating and cooling, and its initial resistance was recorded. The ratio of the initial resistance after 20 cycles to the initial resistance after the first cycle was used to study the effect of the expansion of different polymers on the sensitivity of the prepared fiber-type temperature sensor.

[0033] The sample is within a certain temperature range ( , The average rate of change of length within a given area is the expansion coefficient. ;in, This represents the change in the length of the sample. The initial length of the sample. This represents the change in length at temperature t.

[0034] The results are shown in Table 2.

[0035] Table 2

[0036] As shown in Table 2, the thermal expansion coefficient of the Aramid / PVA / rGO / MnO2 fiber in Example 1 is closer to zero, resulting in higher sensitivity and resistivity recovery. Figure 2As shown, the high reproducibility principle of the fiber-type temperature sensor is as follows: the main reason for the poor reproducibility of thermistor temperature sensors is the irreversible damage to the conductive filler / polymer network, which stems from the expansion or contraction of the polymer matrix with temperature changes. Therefore, adjusting the coefficient of thermal expansion of the polymer to be close to zero can effectively suppress its dimensional deformation under temperature changes, thereby ensuring the stability of the conductive network structure and significantly improving the cyclic reproducibility of the sensor. Within the temperature sensing range, the shape deformation of Aramid / PVA / rGO / MnO2 fibers is minimal, while PVA / rGO / MnO2 and Aramid / rGO / MnO2 fibers exhibit significant shape expansion and contraction, respectively. Aramid / rGO / MnO2 fibers contract with increasing temperature, leading to unpredictable rearrangement of the reduced graphene oxide / manganese dioxide network—potentially increasing contact connections due to cross-arrangement or decreasing connections due to alignment shifting to parallel, ultimately resulting in sensitivity fluctuations. Conversely, PVA / rGO / MnO2 fibers expand with increasing temperature, loosening the thermosensitive reduced graphene oxide / manganese dioxide network structure and reducing or breaking carrier transport paths (leading to an increase in resistance). This significantly conflicts with the inherent negative temperature coefficient (NTC) effect of the reduced graphene oxide / manganese dioxide network (resistance decreases with increasing temperature). Therefore, Aramid / PVA / rGO / MnO2 fibers exhibit more reliable thermosensitivity, and the thermosensitivity of PVA / rGO / MnO2 fibers is consistently lower than that of Aramid / rGO / MnO2 fibers.

[0037] Performance tests were performed on the fabricated fiber-type zinc ion-powered temperature sensor. 1. For example Figure 3 As shown in the electron microscope image of the fiber-type temperature sensor prepared in Example 1, a uniform Ecoflex / boron nitride coating tightly wraps the thermistor fiber core, and the coating exhibits a micro / nanoporous structure. Elemental analysis of the temperature sensor cross-section by energy dispersive spectroscopy revealed the presence of carbon, nitrogen, manganese, and boron, which correspond to reduced graphene oxide, polyvinyl alcohol, aramid fiber, manganese dioxide, and boron nitride, respectively. The carbon element originates from reduced graphene oxide and polyvinyl alcohol.

[0038] 2. For example Figure 4Figure 4a shows an electron microscope image of the fiber-type zinc-ion battery prepared in Example 1. Ecoflex encapsulation not only ensures the smoothness of the battery surface but also effectively improves the battery's lifespan and structural stability. Notably, the polyacrylamide gel electrolyte has a dual function, acting as both a solid electrolyte and a separator. It not only achieves efficient ion transport but also physically isolates the manganese dioxide-modified carbon fiber positive electrode from the zinc wire negative electrode, while simultaneously bonding them together to form a fully integrated fiber-like battery. The cross-sectional view shows a tight bond between the polyacrylamide gel, zinc wire, and manganese dioxide-modified carbon fiber. Figure 4 b). The uniform distribution of manganese in the EDS further confirms that the manganese dioxide layer is uniformly coated on the carbon fiber surface. Figure 4 c).

[0039] 3. For example Figure 5 As shown, the fiber-type temperature sensor prepared by this invention exhibits minimal thermal deformation, maintaining the integrity of the reduced graphene oxide / manganese dioxide network. After 20 heating and cooling cycles, the thermal sensitivity of the temperature sensor remained almost unchanged, further confirming its high reproducibility and reliability. Figure 5 a). Furthermore, the temperature sensor can successfully detect temperature changes as low as 0.1℃. Figure 5 b).

[0040] 4. For example Figure 6 As shown, the open-circuit voltage of the fiber-type zinc-ion battery prepared by this invention is as high as 1.49V ( Figure 6 a). The cyclic voltammetry curves show distinct redox peaks at approximately 1.68 V and 1.35 V, which are well maintained at different scan rates, indicating excellent electrochemical reversibility. Figure 6 b). This battery also exhibits good rate performance ( Figure 6 c).

[0041] 5. For example Figure 7 As shown, the fiber-type temperature sensor prepared by this invention can test six materials with different thermal conductivity at an initial temperature of 40°C. Figure 7 The relative resistance change of the sensor shows a clear linear relationship with the thermal conductivity of the material, which confirms that the sensor has excellent thermal sensitivity and responsiveness.

[0042] 6. For example Figure 8As shown, the fiber-type temperature sensor prepared by this invention can be easily integrated into textiles and powered by a flexible fiber-type zinc-ion battery for human body temperature detection. When the sensor is sewn into the collar of clothing, the temperature readings it collects are in high agreement with the measurement results of an infrared thermal imager, confirming that the sensor has excellent accuracy and responsiveness in practical wearable scenarios (8a). The sensor can also effectively track the body temperature changes of athletes in different physical states such as rest, walking, and running (8a). Figure 8 b). During a 5-minute running session, the body temperature curve recorded by this sensor was highly consistent with the trend of commercially available sensors. Figure 8 c). Furthermore, the sensor can be conveniently placed under the armpit to quickly and accurately detect fever-related temperature fluctuations (including high fever, moderate fever, low fever, and normal body temperature). Figure 8 (d and 8e). After the sensor was continuously powered for more than 4 hours, the output voltage of the fibrous ZIB only dropped slightly from 4V to 3.5V, demonstrating stable discharge performance. Figure 8 f). Simultaneously, its fast-charging capability enables rapid energy recovery, ensuring continuous operation to meet the needs of long-term health monitoring.

[0043] The fiber-type zinc-ion powered temperature sensor prepared in this invention can be integrated into clothing to monitor body temperature in real time during exercise and detect early fever based on subtle thermal changes. The fiber-type temperature sensor has a near-zero coefficient of thermal expansion, and combined with a highly conductive network constructed from reduced graphene oxide and manganese dioxide, it effectively suppresses signal drift caused by temperature changes, exhibiting good stability and reproducibility. Ecoflex / boron nitride not only possesses high thermal conductivity and water retention properties (maintaining fiber flexibility), but also effectively prevents moisture from affecting the sensing performance. The fiber-type zinc-ion battery is fabricated using an integrated method, eliminating the need for complex assembly steps, exhibiting stable discharge performance, and its fast-charging capability enables rapid energy recovery, ensuring continuous operation to meet the needs of long-term health monitoring.

[0044] The above description is only a preferred embodiment of the present invention and is 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 fiber-type zinc ion powered temperature sensor, characterized in that, The temperature sensor powered by the fiber-type zinc-ion battery is made by integrating a fiber-type temperature sensor with a fiber-type zinc-ion battery.

2. The fiber-type zinc ion powered temperature sensor according to claim 1, characterized in that, The fiber-type temperature sensor is made by wet spinning and encapsulating a thermosensitive mixture with an Ecoflex / boron nitride coating.

3. The fiber-type zinc ion powered temperature sensor according to claim 2, characterized in that, The thermosensitive mixture is prepared by dissolving aramid and polyvinyl alcohol in a dimethylacetamide / lithium chloride mixed solvent and then incorporating reduced graphene oxide and manganese dioxide.

4. The fiber-type zinc ion powered temperature sensor according to claim 1, characterized in that, The fiber-type zinc-ion battery is prepared by injecting a polyacrylamide electrolyte solution containing zinc sulfate and manganese sulfate between a carbon fiber positive electrode and a zinc wire negative electrode, followed by ultraviolet light polymerization and Ecoflex encapsulation.

5. A fiber-type zinc ion powered temperature sensor according to claim 4, characterized in that, The carbon fiber cathode is prepared by coating carbon fiber with a mixed slurry of carbon black, manganese dioxide, and polyvinylidene fluoride.

6. A method for fabricating a fiber-type zinc ion powered temperature sensor, characterized in that, The preparation steps include the following: (1) Mix dimethylacetamide and lithium chloride solution at a mass ratio of 1:2~6, stir at 200~300 r / min for 10~30 min at 25~30℃ to obtain a mixed solvent; mix aramid and polyvinyl alcohol at a mass ratio of 1:0.1~0.4, add to the mixed solvent at a solid-liquid ratio of 1:10~14, stir at 200~300 r / min for 4 h at 85~105℃ to obtain a polymer solution; mix reduced graphene oxide and manganese dioxide at a mass ratio of 3~5:1, add to the polymer solution at a solid-liquid ratio of 1:14~15 and continue stirring for 1 h to obtain a thermosensitive mixture; transfer the thermosensitive mixture to a syringe, inject it into a water bath at a rate of 3~7 mL / h through a wet spinning machine, take out the obtained fiber, wash it with deionized water 3~5 times, and dry it at 50~70℃ for 20~40 min to obtain Aramid / PVA / rGO / MnO2 fiber; Ecoflex and boron nitride were mixed evenly at a mass ratio of 1:0.1~0.4 to prepare a coating mixture. Aramid / PVA / rGO / MnO2 fibers were immersed in the coating mixture for 3~7 minutes, pulled up and left to stand at room temperature for 20~40 minutes to level, and dried at 25~30℃ for 1~3 hours to prepare a fiber-type temperature sensor. (2) Carbon black, manganese dioxide, polyvinylidene fluoride and N-methylpyrrolidone solvent are mixed evenly in a mass ratio of 1:(0.15~0.45):(0.05~0.2):(140~160), and ground for 10~30 min to obtain a mixed slurry; conductive carbon fibers are immersed in the mixed slurry for 3~7 min, pulled up and dried at 70~90℃ for 0.5~1.5 h to obtain manganese dioxide modified carbon fiber positive electrode; acrylamide, ammonium persulfate, N,N-methylenebisacrylamide, tetramethylethylenediamine and deionized water are mixed evenly in a mass ratio of 1:(0.005~0.007):(0.005~0.007):(0.006~0.008):(4~6). Mix 1.75-2.25 mol / L zinc sulfate and 0.1-0.3 mol / L manganese sulfate, and stir at 200-300 r / min for 20-40 min at 25-30℃ to obtain a polyacrylamide electrolyte solution. Fix manganese dioxide-modified carbon fiber positive electrode and zinc wire negative electrode parallel to both sides of the inner wall of a polyvinyl chloride hose, inject the polyacrylamide electrolyte solution until the electrodes are submerged, and irradiate under 365 nm ultraviolet light for 1-5 min to obtain a polyacrylamide gel electrolyte. Peel the polyacrylamide gel electrolyte from the polyvinyl chloride hose mold, immerse it in Ecoflex for 3-7 min, pull it out, and dry it at 25-30℃ for 1.5-2.5 h to obtain a fiber-type zinc-ion battery. (3) The fiber-type temperature sensor is connected to the printed circuit board through wires to form the basic link for signal transmission and processing; the fiber-type zinc-ion battery is connected to the DC-DC converter to provide a constant voltage to the sensor and then connected to the printed circuit board to obtain the fiber-type zinc-ion powered temperature sensor.

7. The method for preparing a fiber-type zinc ion powered temperature sensor according to claim 6, characterized in that, In step (1), the aramid is 1313 short-cut fiber, the polyvinyl alcohol is type 124, the reduced graphene oxide is multilayer reduced graphene oxide, the Ecoflex is type 00-30, and the boron nitride size is 1μm.

8. The method for fabricating a fiber-type zinc ion powered temperature sensor according to claim 6, characterized in that, The syringe mentioned in step (1) is a 10mL syringe with a needle diameter of 1.8mm.

9. The method for preparing a fiber-type zinc ion powered temperature sensor according to claim 6, characterized in that, The carbon black in step (2) is Super P Li carbon black, polyvinylidene fluoride with a molecular weight of 90,000, conductive carbon fiber with a model of T300-1K, and zinc wire with a size of 0.5mm.

10. The application of a fiber-type zinc ion powered temperature sensor according to any one of claims 1 to 5 in medical health monitoring and diagnosis.

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