Multifunctional film for intelligent wearing and preparation method thereof
By alternately layering graphene carbon nanotubes and silver nanoparticles using electrospinning and hot pressing techniques, the problem of adding silver nanoparticles to multifunctional heating films has been solved, achieving efficient heating, infrared therapy, and sterilization functions, making it suitable for smart wearable devices.
Patent Information
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2025-08-18
- Publication Date
- 2026-03-31
AI Technical Summary
In existing technologies, it is difficult to add nano-silver to graphene carbon nanotube slurry, resulting in high cost and complex process in the preparation of multifunctional heating films, and it is difficult to combine sterilization function, which limits their application in smart wearable devices.
A multifunctional film with heating, infrared therapy, and sterilization functions was prepared by alternately stacking graphene carbon nanotube layers and silver nanolayers using electrospinning technology and combining it with hot pressing. The uniform composite structure formed by electrospinning avoids the agglomeration of silver nanolayers and reduces production costs.
It achieves efficient electrothermal conversion, stable heating and antibacterial effects of multifunctional thin films, simplifies the preparation process, reduces production costs, and is suitable for large-scale industrial production.
Smart Images
Figure CN121756700A_ABST
Abstract
Description
Technical Field
[0001] This invention relates to the field of smart wearable materials technology, specifically to a multifunctional thin film for smart wearables and its preparation method. Background Technology
[0002] As a rapidly developing emerging industry in recent years, smart wearable devices rely heavily on various high-performance thin film materials to realize their core functions. In particular, in the field of heated clothing, the performance of the heating film directly determines the user experience and functional expansion of the product.
[0003] Currently, the materials used in heating films are undergoing rapid iteration from traditional to novel types. Traditional heating films mostly use materials such as metal wires, silicon carbide, and carbon fibers. These materials have limited functions, only providing basic heating. With advancements in materials science, novel materials such as graphene, carbon nanotubes, polypyrrole, and silver nanowires are gradually being applied to the field of heating films, giving them more additional functions. Among them, films with added graphene and carbon nanotubes can release far-infrared rays during heating, thus achieving infrared therapy functions; while the introduction of silver nanowires endows the films with antibacterial properties. This allows heating films to simultaneously possess multiple functions such as heating, infrared therapy, and sterilization, greatly enhancing the practicality of smart wearable devices.
[0004] However, existing technologies still have significant drawbacks in preparing such multifunctional films. On the one hand, the current methods for forming graphene carbon nanotube heating films are mainly CVD film formation or slurry coating. CVD film formation is complex and costly, and is only suitable for high-end brand clothing, making it difficult to achieve large-scale adoption. Slurry coating requires extremely high precision in slurry formulation, necessitating the addition of a large amount of additives to ensure the slurry flows and spreads on the substrate, which not only increases the difficulty of preparation but may also affect the performance stability of the film. On the other hand, while nano-silver is an effective bactericide, it is difficult to add directly to graphene carbon nanotube slurries due to its tendency to agglomerate during dispersion. This results in most existing conductive heating films lacking bactericidal functions, limiting their application scenarios in the field of smart wearables.
[0005] Therefore, developing a thin film material that can solve the problem of nano-silver dispersion, simplify the preparation process, and combine heating, infrared therapy, and sterilization functions has become an urgent technical problem to be solved in the field of smart wearables. Summary of the Invention
[0006] Technical problems to be solved
[0007] To address the shortcomings of existing technologies, this invention provides a multifunctional thin film for smart wearables and its preparation method, solving the problems of difficulty in adding nano-silver to graphene carbon nanotube slurry, high cost of CVD method, and high requirements for slurry of coating method.
[0008] Technical solution
[0009] To achieve the above objectives, the present invention is implemented through the following technical solution: a multifunctional thin film for smart wearables, wherein the thin film is formed by alternating layers of graphene carbon nanotubes and nano-silver layers, and has toughness after hot pressing, and a sheet resistance ≤25Ω;
[0010] The graphene carbon nanotube layer is formed by electrospinning a graphene carbon nanotube composite dispersion, and the nano silver layer is formed by electrospinning a spinning solution containing silver nitrate.
[0011] The raw materials for preparing the graphene-carbon nanotube composite dispersion include NMP solution of polyvinylpyrrolidone (K30), single-layer graphene powder, and oligowalled carbon nanotube powder.
[0012] The raw materials for preparing the silver nitrate-containing spinning solution include an NMP solution of polyvinylpyrrolidone (K30) and solid silver nitrate.
[0013] Preferably, the preparation process of the graphene-carbon nanotube composite dispersion is as follows: take 100g of 30% NMP solution of polyvinylpyrrolidone (K30), slowly add 5-20g of monolayer graphene powder, sonicate with a cell disruptor for 30 minutes, then slowly add 10-20g of oligowalled carbon nanotube powder, continue to sonicate with a cell disruptor for 60 minutes, and then disperse and grind with a high-pressure homogenizer until the average particle size of the dispersion is ≤0.5um.
[0014] Preferably, the preparation process of the spinning solution containing silver nitrate is as follows: take 0.5 g of 99% silver nitrate solid and add it to 99.5 g of 30% NMP solution of polyvinylpyrrolidone (K30), and stir continuously at 70°C for 2 h until it becomes clear.
[0015] Preferably, the alternating stacking is performed 20 times, and the hot pressing treatment is performed at 150°C using hot rollers.
[0016] Preferably, the electrospinning process conditions are: spinning voltage 17KV, receiving distance 12cm, and substrate is PET film.
[0017] A method for preparing a multifunctional thin film for smart wearables includes the following steps:
[0018] S1. To prepare a graphene-carbon nanotube composite dispersion, take 100g of 30% NMP solution of polyvinylpyrrolidone (K30), slowly add 5-20g of monolayer graphene powder, sonicate with a cell disruptor for 30 minutes, then slowly add 10-20g of oligowalled carbon nanotube powder, continue to sonicate with a cell disruptor for 60 minutes, and then disperse and grind using a high-pressure homogenizer until the average particle size of the dispersion is ≤0.5um.
[0019] S2. To prepare a spinning solution containing silver nitrate, take 0.5 g of 99% silver nitrate solid and add it to 99.5 g of 30% NMP solution of polyvinylpyrrolidone (K30). Stir continuously at 70°C for 2 h until the solution is clear.
[0020] S3. Using PET film as substrate, under the conditions of spinning voltage of 17KV and receiving distance of 12cm, the graphene carbon nanotube composite dispersion prepared in S1 is first electrospun to form a graphene carbon nanotube layer, and then the spinning solution containing silver nitrate prepared in S2 is electrospun to form a silver nanolayer. This process is repeated 20 times.
[0021] S4. The film obtained in S3 is subjected to hot rolling treatment at 150°C to obtain the multifunctional film.
[0022] Preferably, the amount of single-layer graphene powder added in S1 is 5 grams, and the amount of oligowalled carbon nanotube powder added is 10 grams.
[0023] Preferably, the amount of single-layer graphene powder added in S1 is 15 grams, and the amount of oligowalled carbon nanotube powder added is 15 grams.
[0024] Preferably, the amount of single-layer graphene powder added in S1 is 20 grams, and the amount of oligowalled carbon nanotube powder added is 20 grams.
[0025] Beneficial effects
[0026] This invention provides a multifunctional thin film for smart wearables and its preparation method. It has the following beneficial effects:
[0027] 1. This invention provides a multifunctional thin film for smart wearables and its preparation method. By cleverly combining graphene, carbon nanotubes, and silver nanoparticles, the film simultaneously possesses three functions: heating, infrared therapy, and sterilization. The synergistic effect of graphene and carbon nanotubes ensures high electrothermal conversion efficiency, achieving stable heating; the released far-infrared rays can act on the human body, exerting infrared therapy effects; and the silver nanoparticles, through their antibacterial properties, effectively inhibit bacterial growth on the film surface, solving the problem of bacterial growth in smart wearable devices during long-term use, and significantly improving the product's hygiene, safety, and applicability.
[0028] 2. This invention provides a multifunctional thin film for smart wearables and its preparation method. The film is prepared using an electrospinning combined with hot pressing process, which has significant advantages over existing CVD film formation and slurry coating methods. The electrospinning process uses a high-voltage electric field to form fiber filaments from the dispersion liquid. Combined with alternating spinning technology, it achieves uniform composite of graphene carbon nanotube layers and silver nanolayers, avoiding the agglomeration problem of silver nanoparticles. Hot pressing further improves the toughness of the film, making its water resistance and abrasion resistance superior to films prepared by traditional film formation methods. Simultaneously, this process requires no complex equipment or excessive additives, reducing dependence on raw material formulations, simplifying the preparation process, and helping to reduce production costs, making it suitable for large-scale industrial production. Attached Figure Description
[0029] Figure 1 This is a SEM image of the composite membrane in Example 1 of the present invention;
[0030] Figure 2 This is a SEM image of the composite membrane in Example 2 of the present invention;
[0031] Figure 3 This is a SEM image of Embodiment 3 of the present invention;
[0032] Figure 4 This is a SEM image of Comparative Example 1 of the present invention;
[0033] Figure 5 This is a comparative example 2SEM image of the present invention. Detailed Implementation
[0034] The technical solutions of the embodiments of the present invention will be clearly and completely described below with reference to the accompanying drawings. 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 skilled in the art without creative effort are within the scope of protection of the present invention.
[0035] Example 1
[0036] A method for preparing a multifunctional thin film for smart wearables includes the following steps:
[0037] Step a: Prepare a graphene-carbon nanotube composite dispersion. Prepare a 50% NMP solution of polyvinylpyrrolidone (K30). Take 100g of a 30% K30 solution and slowly add 5g of monolayer graphene powder. Continue to sonicate with a cell disruptor for 30 minutes. Slowly add 10g of oligowalled carbon nanotube powder and sonicate with a cell disruptor for 60 minutes. Disperse and grind the resulting graphene-carbon nanotube mixed dispersion using a high-pressure homogenizer. Use a particle size analyzer to track the particle size of the dispersion until the average particle size is ≤0.5μm.
[0038] Step b: Prepare a 0.5% silver nitrate solution. Take 0.5 g of 99% silver nitrate solid and add it to 99.5 g of the 30% K30 solution prepared in step a. Stir continuously at 70°C for 2 hours until the solution becomes clear to obtain the silver nitrate spinning solution.
[0039] Step c: Using the graphene carbon nanotube dispersion solution prepared in step a as the first layer of electrospinning solution and PET film as the spinning fiber substrate, a graphene carbon nanotube film is prepared under the uniform electrospinning process conditions of 17KV spinning voltage and 12cm receiving distance. Then, the spinning solution is replaced with a spinning solution containing silver nitrate, and a second layer of silver nanoparticles is spun on the graphene carbon nanotube film fiber. This process is repeated to continuously and alternately spin graphene carbon nanotube and silver nanoparticle composite films. After 20 consecutive alternating spinning cycles, the film is removed and hot-pressed with a 150℃ hot roller to form a tough film. The sheet resistance of the film is ≤25Ω by a four-probe test.
[0040] Step d: Perform SEM characterization on the thin film obtained above, such as... Figure 1 As shown, a graphene-carbon nanotube composite conductive film doped with silver nanoparticles was obtained.
[0041] Example 2
[0042] A method for preparing a multifunctional thin film for smart wearables includes the following steps:
[0043] Step a: Prepare a graphene-carbon nanotube composite dispersion. Prepare a 50% NMP solution of polyvinylpyrrolidone (K30). Take 100g of a 30% K30 solution and slowly add 15g of monolayer graphene powder. Continue to sonicate with a cell disruptor for 30 minutes. Slowly add 15g of oligowalled carbon nanotube powder and sonicate with a cell disruptor for 60 minutes. Disperse and grind the resulting graphene-carbon nanotube mixed dispersion using a high-pressure homogenizer. Use a particle size analyzer to track the particle size of the dispersion until the average particle size is ≤0.5μm.
[0044] Step b: Prepare a 0.5% silver nitrate solution. Take 0.5 g of 99% silver nitrate solid and add it to 99.5 g of the 30% K30 solution prepared in step a. Stir continuously at 70°C for 2 hours until the solution becomes clear to obtain the silver nitrate spinning solution.
[0045] Step c: Using the graphene carbon nanotube dispersion solution prepared in step a as the first layer of electrospinning solution and PET film as the spinning fiber substrate, a graphene carbon nanotube film is prepared under the uniform electrospinning process conditions of 17KV spinning voltage and 12cm receiving distance. Then, the spinning solution is replaced with a spinning solution containing silver nitrate to prepare the second layer of silver nanoparticles. This process is repeated to continuously and alternately spin graphene carbon nanotube and silver nanoparticle composite films. After 20 consecutive alternating spinning cycles, the film is removed and hot-pressed with a 150℃ hot roller to form a tough film. The sheet resistance of the film is ≤25Ω by four-probe testing.
[0046] Step d: Perform SEM characterization on the thin film obtained above, such as... Figure 2 As shown, a graphene-carbon nanotube composite conductive film doped with silver nanoparticles was obtained.
[0047] Example 3
[0048] A method for preparing a multifunctional thin film for smart wearables includes the following steps:
[0049] Step a: Prepare a graphene-carbon nanotube composite dispersion. Prepare a 50% NMP solution of polyvinylpyrrolidone (K30). Take 100g of a 30% K30 solution and slowly add 20g of monolayer graphene powder. Continue to sonicate with a cell disruptor for 30 minutes. Slowly add 20g of oligowalled carbon nanotube powder and sonicate with a cell disruptor for 60 minutes. Disperse and grind the resulting graphene-carbon nanotube mixed dispersion using a high-pressure homogenizer. Use a particle size analyzer to track the particle size of the dispersion until the average particle size is ≤0.5μm.
[0050] Step b: Prepare a 0.5% silver nitrate solution. Take 0.5 g of 99% silver nitrate solid and add it to 99.5 g of the 30% K30 solution prepared in step a. Stir continuously at 70°C for 2 hours until the solution becomes clear to obtain the silver nitrate spinning solution.
[0051] Step c: Using the graphene carbon nanotube dispersion solution prepared in step a as the first layer of electrospinning solution and PET film as the spinning fiber substrate, a graphene carbon nanotube film is prepared under the uniform electrospinning process conditions of 17KV spinning voltage and 12cm receiving distance. Then, the spinning solution is replaced with a spinning solution containing silver nitrate to prepare the second layer of silver nanoparticles. This process is repeated to continuously and alternately spin graphene carbon nanotube and silver nanoparticle composite films. After 20 consecutive alternating spinning cycles, the film is removed and hot-pressed with a 150℃ hot roller to form a tough film. The sheet resistance of the film is ≥25Ω by four-probe testing.
[0052] Step d: Perform SEM characterization on the thin film obtained above, such as... Figure 3 As shown, a graphene-carbon nanotube composite conductive film doped with silver nanoparticles was obtained.
[0053] Comparative Example 1
[0054] A method for preparing a thin film includes the following steps:
[0055] Step a: Prepare a graphene-carbon nanotube composite dispersion. Prepare a 50% NMP solution of polyvinylpyrrolidone (K30). Take 100g of a 30% K30 solution and slowly add 5g of monolayer graphene powder. Continue to sonicate with a cell disruptor for 30 minutes. Slowly add 10g of oligowalled carbon nanotube powder and sonicate with a cell disruptor for 60 minutes. Disperse and grind the resulting graphene-carbon nanotube mixed dispersion using a high-pressure homogenizer. Use a particle size analyzer to track the particle size of the dispersion until the average particle size is ≤0.5μm.
[0056] Step b: Using the graphene carbon nanotube dispersion solution prepared in step a as the electrospinning solution and PET film as the spinning fiber substrate, a graphene carbon nanotube film is prepared under the uniform electrospinning process conditions of 17KV spinning voltage and 12cm receiving distance. The graphene carbon nanotube fiber film is spun out. After continuous spinning 20 times, the film is removed and hot-pressed by a 150℃ hot roller to form a tough film. The sheet resistance of the film is ≤25Ω by four-probe testing.
[0057] Step c: Perform SEM characterization on the thin film obtained above, such as... Figure 4 As shown, a graphene-carbon nanotube composite conductive film was obtained.
[0058] Comparative Example 2
[0059] A method for preparing a thin film includes the following steps:
[0060] Step a: Prepare a 0.5% silver nitrate solution. Take 0.5 g of 99% silver nitrate solid and add it to 99.5 g of 30% K30 solution. Stir continuously at 70°C for 2 hours until the solution is clear to obtain silver nitrate spinning solution.
[0061] Step b: Using the nano-silver dispersion solution prepared in step a as the electrospinning solution and PET film as the spinning fiber substrate, nano-silver films are prepared under the uniform electrospinning process conditions of 17KV spinning voltage and 12cm receiving distance. Nano-silver fiber films are spun out. After 40 consecutive spinning cycles, the film is removed and hot-pressed by a 150℃ hot roller to form a tough film. The sheet resistance of the film is ≤25Ω by four-probe testing.
[0062] Step d: Perform SEM characterization on the thin film obtained above, such as... Figure 5 As shown, a nano-silver conductive film was obtained.
[0063] The films prepared in Examples 1-3 and Comparative Examples 1-2 were subjected to performance tests. The results showed that the graphene-carbon nanotube composite conductive films doped with silver nanoparticles prepared in Examples 1 and 2, while having a sheet resistance of ≤25Ω, also exhibited antibacterial rates of over 90% against Escherichia coli and Staphylococcus aureus in the antibacterial ring test. After 50 water washings and rubbing tests, the film structure remained intact, with a sheet resistance change rate of ≤10%, maintaining good conductivity and antibacterial effect. The film prepared in Example 3, due to its higher addition of graphene and carbon nanotubes, had a sheet resistance ≥25Ω, resulting in slightly inferior conductivity, but the antibacterial rate remained above 85%. The graphene-carbon nanotube composite conductive film prepared in Comparative Example 1, although having a sheet resistance ≤25Ω, lacked antibacterial function. The silver nanoparticle conductive film prepared in Comparative Example 2 had a sheet resistance ≤25Ω and an antibacterial rate of over 90%, but after 30 water washings and rubbing tests, the sheet resistance change rate reached 20%, and its toughness and weather resistance were inferior to the films in Examples 1 and 2. The above performance test results are compared with the SEM characterization images of each embodiment and comparative example ( Figure 1-5 The consistent microstructural features exhibited further verify the effectiveness of the technical solution of this invention.
[0064] Although embodiments of the invention have been shown and described, it will be understood by those skilled in the art that various changes, modifications, substitutions and alterations can be made to these embodiments without departing from the principles and spirit of the invention, the scope of which is defined by the appended claims and their equivalents.
Claims
1. A multifunctional film for smart wear, characterized by, The film is formed by alternately stacking graphene carbon nanotube layers and nano-silver layers, and has flexibility and square resistance ≤25Ω after heat pressing treatment. The graphene carbon nanotube layer is formed by electrospinning of a graphene carbon nanotube composite dispersion liquid, and the nano-silver layer is formed by electrospinning of a spinning solution containing silver nitrate. The preparation raw materials of the graphene carbon nanotube composite dispersion liquid include NMP solution of polyvinylpyrrolidone (K30), single-layer graphene powder and oligomeric wall carbon nanotube powder. The preparation raw materials of the spinning solution containing silver nitrate include NMP solution of polyvinylpyrrolidone (K30) and silver nitrate solid. 2.The multifunctional film for smart wear according to claim 1, wherein: The preparation process of the graphene carbon nanotube composite dispersion liquid is as follows: 100 grams of 30% NMP solution of polyvinylpyrrolidone (K30) is slowly added with 5-20 grams of single-layer graphene powder, and then ultrasonic treatment is performed for 30 minutes by using a cell disruptor, and then 10-20 grams of oligomeric wall carbon nanotube powder is slowly added, and then ultrasonic treatment is continuously performed for 60 minutes by using the cell disruptor, and then dispersion grinding is performed by using a high-pressure homogenizer until the average particle size of the dispersion liquid is ≤0.5um. 3.The multifunctional film for smart wear according to claim 1, wherein: The preparation process of the spinning solution containing silver nitrate is as follows: 0.5 grams of 99% silver nitrate solid is added to 99.5 grams of 30% NMP solution of polyvinylpyrrolidone (K30), and then constant stirring is performed for 2 hours at 70℃ until the solution is clear. 4.The multifunctional film for smart wear according to claim 1, wherein: The number of alternately stacking is 20, and the heat pressing treatment condition is 150℃ heat roller heat pressing. 5.The multifunctional film for smart wear according to claim 1, wherein: The process condition of electrospinning is as follows: spinning voltage is 17KV, receiving distance is 12cm, and the substrate is PET film.
6. A method for preparing a multifunctional film for smart wear, characterized by, The method comprises the following steps: S1. Preparation of graphene carbon nanotube composite dispersion liquid, 100 grams of 30% NMP solution of polyvinylpyrrolidone (K30) is slowly added with 5-20 grams of single-layer graphene powder, and then ultrasonic treatment is performed for 30 minutes by using a cell disruptor, and then 10-20 grams of oligomeric wall carbon nanotube powder is slowly added, and then ultrasonic treatment is continuously performed for 60 minutes by using the cell disruptor, and then dispersion grinding is performed by using a high-pressure homogenizer until the average particle size of the dispersion liquid is ≤0.5um; S2. Preparation of spinning solution containing silver nitrate, 0.5 grams of 99% silver nitrate solid is added to 99.5 grams of 30% NMP solution of polyvinylpyrrolidone (K30), and then constant stirring is performed for 2 hours at 70℃ until the solution is clear; S3. Under the conditions of spinning voltage 17KV and receiving distance 12cm, the graphene carbon nanotube composite dispersion liquid prepared in S1 is electrospun to form a graphene carbon nanotube layer, and then the spinning solution containing silver nitrate prepared in S2 is electrospun to form a nano-silver layer, and the above steps are alternately repeated for 20 times; S4. The film obtained in S3 is subjected to 150℃ heat roller heat pressing treatment to obtain the multifunctional film. 7.The method for preparing a multifunctional film for smart wear according to claim 6, characterized in that: The amount of single-layer graphene powder added in S1 is 5 grams, and the amount of oligomeric wall carbon nanotube powder added is 10 grams. 8.The method for preparing a multifunctional film for smart wear according to claim 6, characterized in that: The amount of single-layer graphene powder added in S1 is 15 grams, and the amount of oligomeric wall carbon nanotube powder added is 15 grams. 9.The method for preparing a multifunctional film for smart wear according to claim 6, characterized in that: The amount of single-layer graphene powder added in S1 is 20 grams, and the amount of oligomeric wall carbon nanotube powder added is 20 grams.