Intelligent electrocaloric fabric and preparation method thereof

Abstract

The application provides an intelligent electrocaloric fabric and a preparation method thereof. The fabric comprises: the electrocaloric fabric is composed of a cotton fabric, an graphene oxide layer and a nano-silver layer, the graphene oxide layer is located between the cotton fabric and the nano-silver layer; wherein the graphene oxide accounts for 25% of the fabric weight percentage, and the nano-silver accounts for 2.43% of the fabric weight percentage. The application uses 1,2,3,4-butane tetracarboxylic acid to increase the density of negative charges on the surface of the graphene oxide loaded cotton fabric, which is not only beneficial to the uniform adsorption of silver ions, so that the silver nanoparticles are uniformly distributed on the fabric, but also increases the adsorption amount of silver ions of the graphene oxide loaded cotton fabric, thereby enhancing the conductivity of the fabric and improving the heating performance of the fabric.

Description

Technical Field

[0001] This application belongs to the field of intelligent heating fabric technology, specifically relating to an intelligent electrothermal heating fabric and its preparation method. Background Technology

[0002] Graphene, as an emerging ultrathin two-dimensional material, is a two-dimensional planar crystal structure composed of a single layer of carbon atoms. The carbon atoms are bonded by sp² hybridization to form a single-layer hexagonal honeycomb lattice. It is one of the thinnest and strongest materials in the world to date. Its optical and electrical properties are excellent, which makes it a promising material for electronic devices, catalysis, adsorption and other fields.

[0003] Currently, the commonly used methods for preparing heating fabrics involve heating with iron powder or resistance wire. For example, CN220966996U discloses a self-heating temperature-controlled blanket; CN220109937U discloses a constant-temperature heating patch composed of iron powder heating material, solid-phase change energy storage material, and a heating patch coating layer. Heating devices composed of this type of material are not recyclable and are considered disposable products. CN103173192A further discloses a flexible sheet-like iron heating material and its manufacturing method. This chemical heating material is made by fixing a mixed powder in the fiber gaps of cellulose fibers and synthetic fibers, or by fixing it in the pores of cellulose fibers with an adhesive. The mixed powder includes powdered carbon material and heating iron powder, which improves heating efficiency to some extent, but suffers from uneven heating, poor comfort, large and irreversible material loss, and environmental pollution, making it difficult to adapt to broader development prospects or changing demands. Summary of the Invention

[0004] This application provides a smart electrothermal fabric and its preparation method to solve the above-mentioned technical problems.

[0005] To solve the above-mentioned technical problems, one technical solution adopted in this application is: a method for preparing a smart electrothermal fabric, comprising:

[0006] S1. Take an appropriate amount of graphene oxide in deionized water, and prepare a 5 g / L graphene oxide dispersion by magnetic stirring and sonication;

[0007] S2. The cotton fabric was ultrasonically cleaned with ethanol and deionized water to remove impurities from the fabric surface. The cleaned fabric was then immersed in the graphene oxide dispersion for 20 min and then dried at 80°C. This process was recorded as one cycle. The above operation was repeated 7 times to obtain the graphene oxide-loaded cotton fabric.

[0008] S3. The graphene oxide-loaded cotton fabric is immersed in the finishing solution, dipped and rubbed twice, pre-dried at 80℃ for 5 min, and cured at 120~160℃ for 3 min to obtain the graphene oxide-loaded carboxylic acid cotton fabric.

[0009] S4. Take 0.845 ml of silver nitrate solution and add an appropriate amount of ammonia water to make the precipitate in the solution disappear, so as to prepare silver ammonia solution; wet the graphene oxide-loaded carboxylic acid cotton fabric, immerse it in the silver ammonia solution at room temperature and place it in a water bath shaker to shake evenly for 30 min; add 8.75 mmol of glyoxal and mix evenly, let it stand for 2 h, take it out and dry it at 80℃ for 30 min to obtain silver / graphene oxide-loaded cotton fabric.

[0010] S5. Silver / graphene oxide-loaded cotton fabric was reduced at 90°C for 2 h with a hydrazine hydrate concentration of 30 mL / L and a bath ratio of 0:1 to obtain an electrothermal fabric.

[0011] Furthermore, in step S3, the finishing solution contains 100-150 g / L of 1,2,3,4-butanetetracarboxylic acid and 80-120 g / L of sodium hypophosphite.

[0012] Furthermore, in step S3, the ratio of 1,2,3,4-butanetetracarboxylic acid to sodium hypophosphite is 1.2-1.5:1.

[0013] Furthermore, in step S4, the pH of the silver ammonia solution is 9-10.

[0014] Furthermore, the concentration of the silver nitrate solution is 0.1-0.2 mol / L.

[0015] Furthermore, the molar ratio of silver nitrate to glyoxal is 4:1 to 9.

[0016] Another technical solution adopted in this application is: a smart electrothermal fabric, comprising: the heating fabric is composed of cotton fabric, graphene oxide layer and silver nanoparticle layer, wherein the graphene oxide layer is located between the cotton fabric and the silver nanoparticle layer; 20%-30% of the graphene accounts for 202%-3% of the fabric weight, and the silver nanoparticle accounts for 2-3% of the fabric weight.

[0017] This application also provides a method for manufacturing heated insoles based on the above-mentioned intelligent electrothermal fabric, including:

[0018] The heating fabric is placed in the pre-reserved groove in the forefoot and fixed with hot melt adhesive. At the same time, the GY-BLE39 sensor module is soldered to the flexible ribbon cable. The 3V button battery compartment is connected to the sensor power supply end and fixed to the heel lining with double-sided tape.

[0019] Next, use double-sided tape to fix the sensor to the reserved groove position on the heel. After placing the cable, use polyester thread to sew the cable along the edge of the sensor in a serpentine pattern. Then, apply 704 flexible waterproof insulating glue evenly to the wire interface and sensor surface. Select breathable and skin-friendly mesh fabric and bond it to the base with hot melt glue. Finally, trim the excess edges.

[0020] After the program is entered, the module transmits a temperature signal via Bluetooth after being powered on. Users can then download the "Bluetooth Debugging Assistant" APP on their mobile phones to pair with the module and achieve real-time monitoring of the insole temperature.

[0021] The beneficial effects of this application are as follows: This application utilizes 1,2,3,4-butanetetracarboxylic acid to increase the density of negative charges on the surface of graphene oxide-loaded cotton fabric. This not only facilitates the uniform adsorption of silver ions, resulting in a uniform distribution of silver nanoparticles on the fabric, but also increases the adsorption capacity of silver ions by the graphene oxide-loaded cotton fabric, thereby enhancing the conductivity of the fabric and improving its thermal performance. This application utilizes the interaction between graphene oxide and silver ions to achieve excellent antibacterial properties in the fabric. Tests against Gram-positive Staphylococcus aureus and Gram-negative Escherichia coli showed a clear inhibition zone around the sample. The sample exhibited a 99% inhibition rate against Staphylococcus aureus and a 92% inhibition rate against Escherichia coli, achieving excellent antibacterial performance. Attached Figure Description

[0022] Figure 1 This is a diagram showing the composition of the heating fabric of one embodiment of the intelligent electrothermal heating fabric of this application;

[0023] Figure 2 This is an example of an intelligent heated insole made from the intelligent electrothermal fabric of this application, using a GY-BLE39 Bluetooth temperature sensor.

[0024] Figure 3 This is an example diagram of an intelligent electrothermal insole made from the intelligent electrothermal fabric of this application;

[0025] Figure 4 This is a SEM image of the heating material in Example 2 of the method for preparing the intelligent electrothermal fabric of this application;

[0026] Figure 5 This is a current-time curve measured in a static state in one embodiment of the smart heating insole made of the smart electrothermal fabric of this application;

[0027] Figure 6 This is a current-time curve measured during walking in one embodiment of the smart heating insole made of the smart electrothermal fabric of this application.

[0028] Figure 7 This is a current-time curve measured during running in one embodiment of the smart heated insole made of the smart electrothermal fabric of this application. Detailed Implementation

[0029] To make the objectives, technical solutions, and advantages of the present invention clearer, the present invention will be further described in detail below with reference to specific embodiments.

[0030] Numerous specific details are set forth in the following description in order to provide a full understanding of the invention. However, the invention may also be practiced in other ways than those described herein, and therefore the invention is not limited to the specific embodiments disclosed in the following specification.

[0031] See Figure 1 This application provides a smart electrothermal fabric, which includes: the heating fabric is composed of cotton fabric (such as pure cotton woven fabric, cotton blended fabric, etc.), a graphene oxide layer and a silver nanoparticle layer, wherein the graphene oxide layer is located between the cotton fabric and the silver nanoparticle layer; wherein the graphene oxide accounts for 20%-30% of the weight percentage of the fabric and the silver nanoparticle layer accounts for 2%-3% of the weight percentage of the fabric.

[0032] This application discloses a smart electrothermal fabric and a method for preparing the same smart heated insole, including:

[0033] Take an appropriate amount of graphene oxide in deionized water, and prepare a 5 g / L graphene oxide dispersion by magnetic stirring and sonication.

[0034] The cotton fabric was ultrasonically cleaned with ethanol and deionized water to remove impurities from the fabric surface. The cleaned fabric was then immersed in the above graphene oxide dispersion for 20 min and then dried at 80 °C. This process was recorded as one cycle. The above operation was repeated 7 times to obtain the graphene oxide-loaded cotton fabric.

[0035] The graphene oxide-loaded cotton fabric prepared above was immersed in a finishing solution containing 100-150 g / L 1,2,3,4-butanetetracarboxylic acid and 80-120 g / L sodium hypophosphite (bath ratio of 50:1), subjected to two dips and two nips, pre-dried at 80 ℃ for 5 min, and cured at 120~160 ℃ for 3 min to obtain the graphene oxide-loaded carboxylic acid cotton fabric.

[0036] Take 0.845 ml of 0.1-0.2 mol / L silver nitrate solution, and add an appropriate amount of ammonia water to dissolve the precipitate in the solution to prepare a silver ammonia solution. Wet the graphene oxide-loaded carboxylic acid cotton fabric prepared above, immerse it in the silver ammonia solution at room temperature, and place it in a water bath shaker to shake evenly for 30 min. Add 8.75 mmol of glyoxal, mix well, let stand for 2 h, and then dry at 80 ℃ for 30 min to obtain the silver / graphene oxide-loaded cotton fabric.

[0037] The silver / graphene oxide-loaded cotton fabric prepared above was reduced at 30 mL / L hydrazine hydrate, a liquor ratio of 50:1, and 90 °C for 2 h to obtain an electrothermal fabric.

[0038] The heating fabric is placed in the pre-drilled groove in the forefoot and secured with hot melt adhesive. Simultaneously, the GY-BLE39 sensor module (such as...) is installed. Figure 2 Solder the 3V button battery compartment (with the switch connected in series in the circuit and an external toggle switch) to the sensor power supply terminal and fix it to the heel lining with double-sided tape; (e.g.) Figure 3 Next, use double-sided tape to fix the sensor to the pre-reserved groove on the heel of the foot. After placing the ribbon cable, use polyester thread to sew the ribbon cable along the edge of the sensor in a serpentine pattern. Then, evenly apply 704 flexible waterproof insulating glue to the wire interface and sensor surface. Select breathable and skin-friendly mesh fabric and bond it to the base with hot melt adhesive. Finally, trim the excess edges. After the program is entered, the module is powered on and transmits a temperature signal via Bluetooth. Download the "Bluetooth Debugging Assistant" APP on your mobile phone to pair with it and realize real-time monitoring of the insole temperature.

[0039] Example 1:

[0040] (1) Wet the cotton fabric and immerse it in 5 g / L graphene oxide dispersion and stir for 20 min. Take it out and dry it at 80℃. Repeat the above operation 7 times to obtain graphene oxide / cotton.

[0041] (2) At a bath ratio of 50:1, the graphene oxide / cotton in step (1) was immersed in a finishing solution containing 120 g / L 1,2,3,4-butanetetracarboxylic acid, 100 g / L sodium hypophosphite and 60 g / L dimethyl sulfoxide for 3 min, then dipped and rubbed twice, pre-dried at 80℃ for 5 min, and cured at 120℃ for 3 min to obtain 1,2,3,4-butanetetracarboxylic acid / graphene oxide / cotton;

[0042] (3) Take 0.1 mol / L silver nitrate at a bath ratio of 50:1, add an appropriate amount of ammonia water to it to make the precipitate disappear in the solution to prepare silver ammonia solution. After wetting the 1,2,3,4-butanetetracarboxylic acid / graphene oxide / cotton prepared in step (2), immerse it in silver ammonia solution (pH value = 9~10) at room temperature (20±2℃) and place it in a water bath shaker to shake vigorously for 30 min. Add 1 mL of glyoxal (n(silver nitrate):n(glyoxal) = 4:7) and mix evenly. Let it stand for 2 h, take it out and dry it at 80℃ to obtain silver / 1,2,3,4-butanetetracarboxylic acid / graphene oxide / cotton.

[0043] (4) The silver / 1,2,3,4-butanetetracarboxylic acid / graphene oxide / cotton obtained in step (3) was reduced by hydrazine hydrate at 90°C for 2 hours to prepare silver / 1,2,3,4-butanetetracarboxylic acid / reduced graphene oxide / cotton.

[0044] (5) After welding the flexible ribbon cable to the GY-BLE39 sensor module, connect it to the 3V button battery compartment (including the toggle switch) and fix it to the heel lining; use double-sided tape to fix the sensor to the heel groove, place the ribbon cable in a close fit, sew the ribbon cable in a serpentine pattern with polyester thread, apply 704 waterproof insulating glue, cover with breathable mesh fabric, and trim the edges. After program input, turn on the toggle switch to power on, open the "Bluetooth Debugging Assistant" APP to pair, and realize real-time monitoring of insole temperature.

[0045] Example 2:

[0046] (1) Wet the cotton fabric and immerse it in 5 g / L graphene oxide dispersion and stir for 20 min. Take it out and dry it at 80℃. Repeat the above operation 5 times to obtain graphene oxide / cotton.

[0047] (2) At a bath ratio of 50:1, the graphene oxide / cotton in step (1) was immersed in a finishing solution containing 120 g / L 1,2,3,4-butanetetracarboxylic acid, 100 g / L sodium hypophosphite and 60 g / L dimethyl sulfoxide for 3 min, then dipped and rubbed twice, pre-dried at 80℃ for 5 min, and cured at 130℃ for 3 min to obtain 1,2,3,4-butanetetracarboxylic acid / graphene oxide / cotton;

[0048] (3) Take 0.1 mol / L silver nitrate at a bath ratio of 50:1, add an appropriate amount of ammonia water to it to make the precipitate disappear in the solution to prepare silver ammonia solution. After wetting the 1,2,3,4-butanetetracarboxylic acid / graphene oxide / cotton prepared in step (2), immerse it in silver ammonia solution (pH value = 9~10) at room temperature (20±2℃) and place it in a water bath shaker to shake vigorously for 30 min. Add 1 mL of glyoxal (n(silver nitrate):n(glyoxal) = 4:7) and mix evenly. Let it stand for 2 h, take it out and dry it at 80℃ to obtain silver / 1,2,3,4-butanetetracarboxylic acid / graphene oxide / cotton.

[0049] (4) The silver / 1,2,3,4-butanetetracarboxylic acid / graphene oxide / cotton obtained in step (3) was reduced by hydrazine hydrate at 90°C for 2 hours to prepare silver / 1,2,3,4-butanetetracarboxylic acid / reduced graphene oxide / cotton.

[0050] (5) After welding the flexible ribbon cable to the GY-BLE39 sensor module, connect it to the 3V button battery compartment (including the toggle switch) and fix it to the heel lining; use double-sided tape to fix the sensor to the heel groove, place the ribbon cable in a close fit, sew the ribbon cable in a serpentine pattern with polyester thread, apply 704 waterproof insulating glue, cover with breathable mesh fabric, and trim the edges. After program input, turn on the toggle switch to power on, open the "Bluetooth Debugging Assistant" APP to pair, and realize real-time monitoring of insole temperature.

[0051] Example 3:

[0052] (1) Wet the cotton fabric and immerse it in 5 g / L graphene oxide dispersion and stir for 20 min. Take it out and dry it at 80℃. Repeat the above operation 5 times to obtain graphene oxide / cotton.

[0053] (2) At a bath ratio of 50:1, the graphene oxide / cotton in step (1) was immersed in a finishing solution containing 120 g / L 1,2,3,4-butanetetracarboxylic acid, 100 g / L sodium hypophosphite and 60 g / L dimethyl sulfoxide for 3 min, then dipped and rubbed twice, pre-dried at 80℃ for 5 min, and cured at 130℃ for 3 min to obtain 1,2,3,4-butanetetracarboxylic acid / graphene oxide / cotton;

[0054] (3) Take 0.1 mol / L silver nitrate at a bath ratio of 50:1, add an appropriate amount of ammonia water to it to make the precipitate disappear in the solution to prepare silver ammonia solution. After wetting the 1,2,3,4-butanetetracarboxylic acid / graphene oxide / cotton prepared in step (2), immerse it in silver ammonia solution (pH value = 9~10) at room temperature (20±2℃) and place it in a water bath shaker to shake vigorously for 30 min. Add 1.287 mL of glyoxal (n(silver nitrate):n(glyoxal) = 4:9) and mix evenly. Let it stand for 2 h, take it out and dry it at 80℃ to obtain silver / 1,2,3,4-butanetetracarboxylic acid / graphene oxide / cotton.

[0055] (4) The silver / 1,2,3,4-butanetetracarboxylic acid / graphene oxide / cotton obtained in step (3) was reduced by hydrazine hydrate at 90°C for 2 hours to prepare silver / 1,2,3,4-butanetetracarboxylic acid / reduced graphene oxide / cotton.

[0056] (5) After welding the flexible ribbon cable to the GY-BLE39 sensor module, connect it to the 3V button battery compartment (including the toggle switch) and fix it to the heel lining; use double-sided tape to fix the sensor to the heel groove, place the ribbon cable in a close fit, sew the ribbon cable in a serpentine pattern with polyester thread, apply 704 waterproof insulating glue, cover with breathable mesh fabric, and trim the edges. After program input, turn on the toggle switch to power on, open the "Bluetooth Debugging Assistant" APP to pair, and realize real-time monitoring of insole temperature.

[0057] Example 4:

[0058] (1) Wet the cotton fabric and immerse it in 5 g / L graphene oxide dispersion and stir for 20 min. Take it out and dry it at 80℃. Repeat the above operation 5 times to obtain graphene oxide / cotton.

[0059] (2) At a bath ratio of 50:1, the graphene oxide / cotton in step (1) was immersed in a finishing solution containing 120 g / L 1,2,3,4-butanetetracarboxylic acid, 100 g / L sodium hypophosphite and 60 g / L dimethyl sulfoxide for 3 min, then dipped and rubbed twice, pre-dried at 80℃ for 5 min, and cured at 130℃ for 3 min to obtain 1,2,3,4-butanetetracarboxylic acid / graphene oxide / cotton;

[0060] (3) Take 0.1 mol / L silver nitrate at a bath ratio of 50:1, add an appropriate amount of ammonia water to it to make the precipitate disappear in the solution to prepare silver ammonia solution. After wetting the 1,2,3,4-butanetetracarboxylic acid / graphene oxide / cotton prepared in step (2), immerse it in silver ammonia solution (pH value = 9~10) at room temperature (20±2℃) and place it in a water bath shaker to shake vigorously for 30 min. Add 143 μL of glyoxal (n(silver nitrate):n(glyoxal) = 4:1) and mix evenly. Let it stand for 2 h, take it out and dry it at 80°C to obtain silver / 1,2,3,4-butanetetracarboxylic acid / graphene oxide / cotton.

[0061] (4) The silver / 1,2,3,4-butanetetracarboxylic acid / graphene oxide / cotton obtained in step (3) was reduced by hydrazine hydrate at 90°C for 2 hours to prepare silver / 1,2,3,4-butanetetracarboxylic acid / reduced graphene oxide / cotton.

[0062] (5) After welding the flexible ribbon cable to the GY-BLE39 sensor module, connect it to the 3V button battery compartment (including the toggle switch) and fix it to the heel lining; use double-sided tape to fix the sensor to the heel groove, place the ribbon cable in a close fit, sew the ribbon cable in a serpentine pattern with polyester thread, apply 704 waterproof insulating glue, cover with breathable mesh fabric, and trim the edges. After program input, turn on the toggle switch to power on, open the "Bluetooth Debugging Assistant" APP to pair, and realize real-time monitoring of insole temperature.

[0063] Example 5:

[0064] (1) Wet the cotton fabric and immerse it in 5 g / L graphene oxide dispersion and stir for 20 min. Take it out and dry it at 80℃. Repeat the above operation 5 times to obtain graphene oxide / cotton.

[0065] (2) At a bath ratio of 50:1, the graphene oxide / cotton in step (1) was immersed in a finishing solution containing 120 g / L 1,2,3,4-butanetetracarboxylic acid, 100 g / L sodium hypophosphite and 60 g / L dimethyl sulfoxide for 3 min, then dipped and rubbed twice, pre-dried at 80℃ for 5 min, and cured at 130℃ for 3 min to obtain 1,2,3,4-butanetetracarboxylic acid / graphene oxide / cotton;

[0066] (3) Take 0.1 mol / L silver nitrate at a bath ratio of 50:1, add an appropriate amount of ammonia water to it to make the precipitate disappear in the solution to prepare silver ammonia solution. After wetting the 1,2,3,4-butanetetracarboxylic acid / graphene oxide / cotton prepared in step (2), immerse it in silver ammonia solution (pH value = 9~10) at room temperature (20±2℃) and place it in a water bath shaker to shake vigorously for 30 min. Add 1 mL of glyoxal (n(silver nitrate):n(glyoxal) = 4:7) and mix evenly. Let it stand for 2 h, take it out and dry it at 80℃ to obtain silver / 1,2,3,4-butanetetracarboxylic acid / graphene oxide / cotton.

[0067] (4) The silver / 1,2,3,4-butanetetracarboxylic acid / graphene oxide / cotton obtained in step (3) was reduced by hydrazine hydrate at 90°C for 2 hours to prepare silver / 1,2,3,4-butanetetracarboxylic acid / reduced graphene oxide / cotton.

[0068] (5) After welding the flexible ribbon cable to the GY-BLE39 sensor module, connect it to the 3V button battery compartment (including the toggle switch) and fix it to the heel lining; use double-sided tape to fix the sensor to the heel groove, place the ribbon cable in a close fit, sew the ribbon cable in a serpentine pattern with polyester thread, apply 704 waterproof insulating glue, cover with breathable mesh fabric, and trim the edges. After program input, turn on the toggle switch to power on, open the "Bluetooth Debugging Assistant" APP to pair, and realize real-time monitoring of insole temperature.

[0069] Example 6:

[0070] (1) Wet the cotton fabric and immerse it in 5 g / L graphene oxide dispersion and stir for 20 min. Take it out and dry it at 80℃. Repeat the above operation 5 times to obtain graphene oxide / cotton.

[0071] (2) At a bath ratio of 50:1, the graphene oxide / cotton in step (1) was immersed in a finishing solution containing 120 g / L 1,2,3,4-butanetetracarboxylic acid, 100 g / L sodium hypophosphite and 60 g / L dimethyl sulfoxide for 3 min, then dipped and rubbed twice, pre-dried at 80℃ for 5 min, and cured at 160℃ for 3 min to obtain 1,2,3,4-butanetetracarboxylic acid / graphene oxide / cotton;

[0072] (3) Take 0.1 mol / L silver nitrate at a bath ratio of 50:1, add an appropriate amount of ammonia water to it to make the precipitate disappear in the solution to prepare silver ammonia solution. After wetting the 1,2,3,4-butanetetracarboxylic acid / graphene oxide / cotton prepared in step (2), immerse it in silver ammonia solution (pH value = 9~10) at room temperature (20±2℃) and place it in a water bath shaker to shake vigorously for 30 min. Add 1 mL of glyoxal (n(silver nitrate):n(glyoxal) = 4:7) and mix evenly. Let it stand for 2 h, take it out and dry it at 80℃ to obtain silver / 1,2,3,4-butanetetracarboxylic acid / graphene oxide / cotton.

[0073] (4) The silver / 1,2,3,4-butanetetracarboxylic acid / graphene oxide / cotton obtained in step (3) was reduced by hydrazine hydrate at 90°C for 2 hours to prepare silver / 1,2,3,4-butanetetracarboxylic acid / reduced graphene oxide / cotton.

[0074] (5) After welding the flexible ribbon cable to the GY-BLE39 sensor module, connect it to the 3V button battery compartment (including the toggle switch) and fix it to the heel lining; use double-sided tape to fix the sensor to the heel groove, place the ribbon cable in a close fit, sew the ribbon cable in a serpentine pattern with polyester thread, apply 704 waterproof insulating glue, cover with breathable mesh fabric, and trim the edges. After program input, turn on the toggle switch to power on, open the "Bluetooth Debugging Assistant" APP to pair, and realize real-time monitoring of insole temperature.

[0075] See Figure 4 The microscopic structure of the fabric surface was observed using a scanning electron microscope (SEM). Figure 4 A dense and continuous nano-silver layer can be clearly seen covering the surface of the cotton fiber, with no obvious agglomeration. This indicates that through 1,2,3,4-butanetetracarboxylic acid modification and in-situ deposition process, silver nanoparticles are uniformly attached to the surface of the graphene oxide / cotton composite base.

[0076] Table 1 shows the surface temperature test results of the electrothermal fabric and the resulting smart heating insole.

[0077] Table 1 shows the surface temperatures of various embodiments of this application.

[0078]

[0079] Table 1 shows the surface temperatures measured in Examples 1 to 6. As can be seen from the surface temperatures measured in Examples 1, 2, and 6, the surface temperature of the fabric first increases and then decreases with the increase of curing temperature, and the surface temperature is the highest at 42°C when the curing temperature is 130°C. As can be seen from Examples 2 to 4, the surface temperature increases with the increase of glyoxal content, and the highest surface temperature is obtained when the molar ratio is 4:7.

[0080] As shown in Table 2, the surface temperature of the electrothermal insole was tested: under an applied voltage of 3V, the temperature was tested using an infrared digital camera, and the surface temperature change of the sample was observed and recorded every 30 seconds for 4 minutes.

[0081] Table 2 shows the surface temperature of the smart heated insole after 4 minutes.

[0082]

[0083] As shown in Table 2, under an applied voltage of 3 V, the surface temperature of the insole exhibits a pattern of rapid rise followed by a gradual plateau within 4 minutes: the temperature rises rapidly from 32.1 ℃ to 40.0 ℃ in the first 120 s, which is the stage with the fastest heating rate (approximately 0.66 ℃ / s); the heating rate slows down from 120 to 180 s, with an average temperature increase of approximately 0.053 ℃ / s; and the temperature enters a plateau period from 180 to 240 s, approaching a thermal equilibrium state.

[0084] Repeatedly wetting and immersing cotton fabric in a graphene oxide dispersion and then drying it ensures that the graphene oxide adheres evenly to the fabric. Without this repeated treatment, the fabric will eventually suffer from uneven heating and low heating efficiency. In the two-dip and two-nip finishing solution, 1,2,3,4-butanetetracarboxylic acid is used to increase the density of negative charges on the graphene oxide / cotton surface. This not only facilitates the uniform adsorption of silver ions, resulting in a uniform distribution of silver nanoparticles on the fabric, but also increases the amount of silver ions adsorbed by the graphene oxide / cotton, thereby enhancing the conductivity of the fabric. The condensation reaction between hydrazine hydrate and 1,2,3,4-butanetetracarboxylic acid improves the adhesion of graphene oxide and silver ions to the fabric, overcoming the problem of ordinary heat-generating fabrics being not washable. Hydrazine hydrate can also respond sensitively to graphene electrodes and quickly reach steady-state current. If 1,2,3,4-butanetetracarboxylic acid is not used in the experiment, the dispersibility and stability of graphene oxide will decrease, which will lead to poor heating uniformity, low efficiency, and even failure to form a continuous path when heating, resulting in local overheating or short circuit.

[0085] Figure 4-6 The current-time curves of the smart heated insole made of heated fabric under static, walking, and running conditions show a clear pattern: the current change is relatively gradual when stationary, the frequency and amplitude of current fluctuations increase significantly during walking, and the fluctuations are more intense and violent during running. Heating efficiency is highly correlated with the body's movement state—the greater the exercise intensity and the faster the movement rhythm, the stronger the current fluctuations. These three curves verify the stability of the smart heating device application and provide a reference direction for subsequent optimization of product heating control and intelligent monitoring and adjustable technologies.

[0086] The heating fabric of this application exhibits excellent heating performance. By utilizing 1,2,3,4-butanetetracarboxylic acid to increase the density of negative charges on the surface of the graphene-loaded cotton fabric, not only is it beneficial for the uniform adsorption of silver ions, resulting in a uniform distribution of silver nanoparticles on the fabric, but it also increases the amount of silver ions adsorbed by the graphene-loaded cotton fabric, thereby enhancing the fabric's conductivity and thus improving its heating performance. Under an applied voltage of 3V, the temperature can rise to 42℃ within 2 minutes, which is very comfortable for most people. In contrast, traditional heating fabrics use different blending ratios of viscose and polyester to achieve a warming effect, but the manufacturing process is extremely complex, the blending ratio is difficult to control, the cost is high, and the heating performance is unstable.

[0087] The heating fabric of this application utilizes the interaction of graphene oxide and silver ions to achieve excellent antibacterial properties. Tests with Gram-positive Staphylococcus aureus and Gram-negative Escherichia coli showed a clear inhibition zone around the sample. The sample demonstrated a 99% inhibition rate against Staphylococcus aureus and a 92% inhibition rate against Escherichia coli, achieving excellent antibacterial performance. Traditional antibacterial agents, on the other hand, adhere to the fiber surface through physical adsorption or simple bonding, and are easily detached under repeated washing or mechanical friction. Furthermore, graphene is renewable, readily available, and less expensive than metals and metal oxides, making it widely used in antibacterial materials.

[0088] The intelligent electrothermal insole made from the heating fabric of this application has good breathability and causes little change to the thickness of the cotton fabric itself. In contrast, most heating insoles on the market use sponge, which is not breathable and has poor comfort, making them unsuitable for outdoor sports.

[0089] This application innovatively develops a heating device that monitors temperature in real time and is easy to wear, enabling remote temperature monitoring, effectively reducing the risk of hypothermia, and maintaining the stability of the human body's core temperature.

[0090] The above description is merely an embodiment of this application and does not limit the patent scope of this application. Any equivalent structural or procedural transformations made using the content of this application's specification and drawings, or direct or indirect applications in other related technical fields, are similarly included within the patent protection scope of this application.

Claims

1. A method for preparing a smart electrothermal fabric, characterized in that, include: S1. Take an appropriate amount of graphene oxide in deionized water, and prepare a 5 g / L graphene oxide dispersion by magnetic stirring and sonication; S2. The cotton fabric was ultrasonically cleaned with ethanol and deionized water to remove impurities from the fabric surface. The cleaned fabric was then immersed in the graphene oxide dispersion for 20 min and then taken out and dried at 80°C. This process was recorded as one cycle. The above operation was repeated 7 times to obtain the graphene oxide-loaded cotton fabric. S3. The graphene oxide-loaded cotton fabric is immersed in the finishing solution, dipped and rubbed twice, pre-dried at 80°C for 5 min, and cured at 120~160°C for 3 min to obtain the graphene oxide-loaded carboxylic acid cotton fabric. S4. Take 0.845 ml of silver nitrate solution and add an appropriate amount of ammonia water to make the precipitate in the solution disappear, so as to prepare silver ammonia solution; wet the graphene oxide-loaded carboxylic acid cotton fabric, immerse it in silver ammonia solution at room temperature and place it in a water bath shaker to shake evenly for 30 min; add 8.75 mmol of glyoxal and mix evenly, let it stand for 2 h, take it out and dry it at 80℃ for 30 min to obtain silver / graphene oxide-loaded cotton fabric. S5. The silver / graphene oxide-loaded cotton fabric was reduced at 30 mL / L hydrazine hydrate, a liquor ratio of 50:1, and 90°C for 2 h to prepare the electrothermal fabric.

2. The method according to claim 2, characterized in that, In step S3, the finishing solution contains 100-150 g / L of 1,2,3,4-butanetetracarboxylic acid and 80-120 g / L of sodium hypophosphite.

3. The method according to claim 2, characterized in that, In step S3, the ratio of 1,2,3,4-butanetetracarboxylic acid to sodium hypophosphite is 1.2-1.5:

1.

4. The method according to claim 2, characterized in that, In step S4, the pH of the silver ammonia solution is 9-10.

5. The method according to claim 2, characterized in that, The concentration of the silver nitrate solution is 0.1-0.2 mol / L.

6. The method according to claim 2, characterized in that, The molar ratio of silver nitrate to glyoxal is 4:1 to 9.

7. A heat-generating fabric prepared by the preparation method according to any one of claims 1-6, characterized in that, The heating fabric is composed of cotton fabric, a graphene oxide layer, and a silver nanoparticle layer, with the graphene oxide layer located between the cotton fabric and the silver nanoparticle layer; wherein the graphene oxide accounts for 20%-30% of the fabric weight and the silver nanoparticle layer accounts for 2%-3% of the fabric weight.

8. A method for manufacturing heated insoles from heated fabric prepared according to any one of claims 1-6, characterized in that, include: The heating fabric is placed in the pre-reserved groove in the forefoot and fixed with hot melt adhesive. At the same time, the GY-BLE39 sensor module is soldered to the flexible ribbon cable. The 3V button battery compartment is connected to the sensor power supply end and fixed to the heel lining with double-sided tape. Next, use double-sided tape to fix the sensor to the reserved groove position on the heel. After placing the cable, use polyester thread to sew the cable along the edge of the sensor in a serpentine pattern. Then, apply 704 flexible waterproof insulating glue evenly to the wire interface and sensor surface. Select breathable and skin-friendly mesh fabric and bond it to the base with hot melt glue. Finally, trim the excess edges. After the program is entered, the module transmits a temperature signal via Bluetooth after being powered on. Users can download the "Bluetooth Debugging Assistant" APP on their mobile phones to pair with the module and achieve real-time monitoring of the insole temperature.

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