Silk-based flexible energy storage fabric and preparation method thereof
By preparing nickel-cobalt hydroxide composite black phosphorus nanosheets in situ on silk fabrics, combining silk silk glue and carbon nanotube conductive paste, the problems of easy oxidation and unsolid load of black phosphorus nanosheets are solved, and efficient preparation of flexible energy storage fabrics is achieved, improving electrochemical and mechanical properties.
Patent Information
- Application Number
- CN202410247638.9
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2024-03-05
- Publication Date
- 2025-09-05
AI Technical Summary
In the prior art, the preparation conditions of black phosphorus nanosheets are harsh and easy to oxidize, resulting in reduced electrochemical performance, and lack of interaction between the fabric and nickel-cobalt hydroxide composite black phosphorus nanosheets, making it difficult to carry out a firm load, resulting in cumbersome preparation process and poor performance of flexible energy storage fabrics.
The nickel-cobalt hydroxide composite black phosphorus nanosheets were prepared in situ on silk fabrics by electrochemical peeling method, and a high-conductive paste was formed on the fabric through the conductive adhesive of silk serigament and carbon nanotubes, thereby achieving the load of the nickel-cobalt hydroxide composite black phosphorus nanosheets, simplifying the preparation process and improving electrochemical performance.
A good synergistic effect was achieved between nickel cobalt hydroxide composite black phosphorus nanosheets and silk fabrics, which improved the electrochemical and mechanical properties of the flexible energy storage fabrics, simplified the preparation process and reduced costs.
Smart Images
Figure CN120592041A_ABST
Abstract
Description
Technical Field
[0001] The present invention belongs to the field of functional fabrics, and in particular relates to a nickel-cobalt hydroxide composite black phosphorus modified silk fabric for electrochemical energy storage, a preparation method thereof, and applications thereof. Background Art
[0002] In recent years, with the rapid development of flexible electronic devices, the demand for flexible energy storage functionalized fabrics with high energy density and high power density has also increased. Nickel cobalt hydroxide provides excellent energy storage through the redox reaction of transition metals. Black phosphorus, as a two-dimensional material, can serve as a supporting skeleton and growth site for nickel cobalt hydroxide on the basis of providing a certain amount of energy storage. Currently, chemical vapor deposition (CVD), (Nanotechnology 2016, 27, 215602.) pulsed laser deposition (PLD), (Adv. Mater. 2015, 27, 3748.) mechanical exfoliation, (ACS Nano 2014, 8, 4033.) liquid exfoliation, (Adv. Mater. 2015, 27, 1887.) and electrochemical exfoliation (Angew. Chem. Int. Edit. 2018, 57, 4677.) are mostly used to exfoliate black phosphorus and composite it with active materials. However, all of the above methods have the following problems: (1) The preparation conditions of black phosphorus nanosheets are harsh and they are easily oxidized during the preparation process, which reduces the electrochemical performance. (2) The multi-step composite process is cumbersome and complex, with a long processing flow, which increases the preparation cost. The lack of interaction between the fabric and the nickel cobalt hydroxide composite black phosphorus nanosheets makes it difficult to firmly load them.
[0003] Therefore, in order to overcome the problems of functional deficiency and complicated process in the current preparation of energy storage fabrics, it is urgent to develop a simpler and more effective preparation method to achieve the excellent electrochemical and mechanical properties of nickel cobalt hydroxide composite black phosphorus modified silk fabrics. Summary of the Invention
[0004] The purpose of the present invention is to provide a silk-based flexible energy storage fabric and a preparation method to address the problems of cumbersome current energy storage fabric processing methods and poor electrochemical and mechanical properties of functionalized fabrics.
[0005] To achieve the above object, according to the first aspect of the present invention, the present invention adopts the following technical solutions:
[0006] A silk-based flexible energy storage fabric, wherein the fabric is a silk fabric or a mixed fabric containing silk, and is characterized in that the fabric has a structure in which nickel cobalt hydroxide composite black phosphorus nanosheets wrap the fabric, the black phosphorus presents a nanosheet structure with 1 to 10 layers, and nickel cobalt hydroxide grows on the nanosheets in the form of particles; wherein the nickel cobalt hydroxide composite black phosphorus nanosheets are loaded on the fabric by reconstructing silk sericin.
[0007] Furthermore, the fabric thickness is 0.5 to 5 mm, and the fabric structure is woven silk fabric and knitted silk fabric.
[0008] To achieve the above object, according to the second aspect of the present invention, the present invention adopts the following technical solutions:
[0009] The method for preparing a silk-based flexible energy storage fabric is characterized by comprising the following specific steps:
[0010] (1) Preparation of active material: nickel source and cobalt source are dissolved in a polar solvent, and black phosphorus is electrochemically stripped using an electrochemical workstation. At the same time, nickel cobalt hydroxide particles are electrodeposited on black phosphorus nanosheets, where black phosphorus serves as the working electrode, to obtain nickel cobalt hydroxide composite black phosphorus nanosheets with 1 to 10 layers.
[0011] (2) Preparation of conductive adhesive: Silk sericin is used as the adhesive and carbon nanotubes as the conductive agent, and the two are mixed by ultrasonic crushing to prepare a highly conductive adhesive slurry;
[0012] (3) Fabric surface cleaning: The fabric material was immersed in deionized water and ethanol for ultrasonic cleaning to remove surface impurities and grease, and then vacuum dried for loading active materials;
[0013] (4) Loading of active materials: The conductive adhesive obtained in step (2) is loaded on the fabric by vacuum filtration to form a highly conductive fabric, and then nickel cobalt hydroxide composite black phosphorus nanosheets are loaded on the highly conductive fabric by vacuum filtration to complete the loading of the active materials.
[0014] Furthermore, the nickel source includes nickel chloride, nickel nitrate, and nickel sulfate, and the cobalt source includes cobalt chloride, cobalt nitrate, and cobalt sulfate; and the solvents for dissolving the nickel source and the cobalt source include deionized water, formamide, ethanol, glycerol, and propylene glycol.
[0015] Furthermore, the method for electrochemical stripping of black phosphorus using an electrochemical workstation is a constant potential method of the electrochemical workstation, with a voltage set to -4 to -25 volts and a duration of 100 to 20,000 seconds.
[0016] Furthermore, in step (2), the ultrasonic power is set to 10-50%, and the ultrasonic time is set to 10-120 minutes.
[0017] Furthermore, in step (3), a mixed solution of deionized water and ethanol in a volume ratio of 1:10 to 10:1 is ultrasonically treated for 10 to 50 minutes to remove particulate impurities and grease on the surface of the fabric, and the fabric is washed with deionized water and dried in a vacuum oven at 40°C to obtain a fabric substrate with a clean surface.
[0018] Furthermore, in step (4), the filtration time is 10 to 20 minutes.
[0019] Furthermore, the concentration range of the added nickel source is 1 mmol / L to 1 mol / L, and the concentration range of the added cobalt source is 1 mmol / L to 1 mol / L.
[0020] Furthermore, the mass ratio of sericin to carbon nanotubes is 1:10 to 10:1.
[0021] Furthermore, the loading amount of the adhesive prepared by sericin and carbon nanotubes on the fabric surface is 1 mg cm -2 ~100mgcm -2 The loading amount of nickel cobalt hydroxide composite black phosphorus nanosheets on the fabric is 1 mg cm -2 ~100mg cm -2 .
[0022] The energy storage fabric of the present invention has a structure in which nickel-cobalt hydroxide composite black phosphorus nanosheets wrap silk fibroin fibers. The nickel-cobalt hydroxide composite black phosphorus nanosheet active material is prepared in situ in a mixed solution of a nickel source and a cobalt source by an electrochemical stripping method. Subsequently, sericin and carbon nanotubes are ultrasonically mixed to prepare a conductive slurry for modifying silk cloth to obtain a conductive fabric. Finally, the nickel-cobalt hydroxide composite black phosphorus nanosheets are loaded on the surface of the carbon nanotube-modified conductive fabric by vacuum filtration to obtain a flexible electrode.
[0023] In summary, the present invention combines nickel cobalt hydroxide with black phosphorus nanosheets through electrochemical exfoliation and then loads them onto fabric via a conductive adhesive. This simple and easy method does not require surface modification of the fabric or the nickel cobalt hydroxide-composite black phosphorus nanosheets, resulting in a functional fabric with excellent energy storage performance. By leveraging the high adhesion of sericin and the high conductivity of carbon nanotubes, the fabric forms a synergistic effect with the highly electrochemically active nickel cobalt hydroxide-composite black phosphorus nanosheets, exhibiting excellent electrochemical performance. This method is expected to find widespread application in flexible energy storage fabrics and flexible electronic devices. BRIEF DESCRIPTION OF THE DRAWINGS
[0024] Figure 1 This is an SEM image of the nickel-cobalt hydroxide composite graphene nanosheets obtained in Example 1.
[0025] Figure 2 This is the surface SEM image of the nickel cobalt hydroxide composite black phosphorus nanosheet modified fabric obtained in Example 1.
[0026] Figure 3 This is the cyclic voltammogram of the nickel cobalt hydroxide composite black phosphorus nanosheet modified fabric obtained in Example 1.
[0027] Figure 4 This is the chronopotentiometry diagram of the nickel cobalt hydroxide composite black phosphorus nanosheet modified fabric obtained in Example 1. DETAILED DESCRIPTION
[0028] The following is an explanation of an embodiment of the present invention: This embodiment is implemented based on the technical solution of the present invention, and a detailed implementation method and operation process are given, but the protection scope of the present invention is not limited to the following embodiment.
[0029] Example 1
[0030] (1) Preparation of active material: 1.2 mmol Ni(NO3)2·6H2O and 1 mmol Co(NO3)2·6H2O were dissolved in 100 mL of deionized water to prepare the electrolyte. The electrolyte was prepared by using a constant potential method in a three-electrode system at -10 V for 2000 s. The working electrode, reference electrode, and counter electrode were black phosphorus, saturated calomel electrode, and platinum sheet, respectively. The obtained nickel cobalt hydroxide composite black phosphorus nanosheet powder was rinsed several times with distilled water and dried in a vacuum oven at 60 °C for 4 h. The SEM image of nickel cobalt hydroxide composite graphene nanosheets can be found in Figure 1 .
[0031] (2) Preparation of conductive adhesive: 100 mg of carbon nanotubes and 50 mg of sericin were added to 20 mL of deionized water to prepare a conductive slurry. The mixture was then ultrasonicated for 30 minutes using an ultrasonicator.
[0032] (3) Fabric surface cleaning: Use a mixed solution of deionized water and ethanol in a volume ratio of 1:1 to ultrasonically remove particulate impurities and grease on the fabric surface. After washing with deionized water, dry it in a vacuum oven at 40°C for 6 hours to obtain a fabric substrate with a clean surface.
[0033] (4) Loading of active materials: The conductive adhesive in (2) was vacuum filtered onto a silk fabric (1×1 cm 2 ) surface to obtain conductive silk fabric, and then nickel cobalt hydroxide composite black phosphorus nanosheets are loaded on the highly conductive silk fabric by vacuum filtration. Figure 2 .
[0034] (5) Electrochemical performance test: The nickel cobalt hydroxide composite black phosphorus modified silk fabric obtained in (4) was subjected to cyclic voltammetry and chronopotentiometry tests to explore the electrochemical properties of the obtained fabric. The results of chronopotentiometry and cyclic voltammetry tests can be found in Figure 3 、 4 .
[0035] Example 2
[0036] (1) Preparation of active material: The electrolyte was prepared by dissolving 1.2 mmol of NiCl2·6H2O and 1 mmol of CoCl2·6H2O in 100 mL of deionized water. A three-electrode system was used with a constant potential at -10 V for 2000 s. The working electrode, reference electrode, and counter electrode were black phosphorus, a saturated calomel electrode, and a platinum sheet, respectively. The resulting nickel-cobalt hydroxide composite black phosphorus nanosheet powder was rinsed several times with distilled water and dried in a vacuum oven at 60°C for 4 h.
[0037] (2) Preparation of conductive adhesive: 100 mg of carbon nanotubes and 50 mg of sericin were added to 20 mL of deionized water to prepare a conductive slurry. The mixture was then ultrasonicated for 30 minutes using an ultrasonicator.
[0038] (3) Fabric surface cleaning: Use a mixed solution of deionized water and ethanol in a volume ratio of 1:1 to ultrasonically remove particulate impurities and grease on the fabric surface. After washing with deionized water, dry it in a vacuum oven at 40°C for 6 hours to obtain a fabric substrate with a clean surface.
[0039] (4) Loading of active materials: The conductive adhesive in (2) was vacuum filtered onto a silk fabric (1×1 cm 2 ) surface is covered to obtain a conductive silk fabric, and then nickel cobalt hydroxide composite black phosphorus nanosheets are loaded on the highly conductive silk fabric by vacuum filtration.
[0040] (5) Electrochemical performance test: The nickel cobalt hydroxide composite black phosphorus modified silk fabric obtained in (4) was subjected to cyclic voltammetry, chronopotentiometry, and AC impedance spectroscopy to explore the electrochemical properties of the obtained fabric.
[0041] Example 3
[0042] (1) Preparation of active material: The electrolyte was prepared by dissolving 1.2 mmol of Ni(SO4)2·6H2O and 1 mmol of Co(SO4)2·6H2O in 100 mL of deionized water. A three-electrode system was used with a constant potential at -10 V for 2000 s. The working electrode, reference electrode, and counter electrode were black phosphorus, a saturated calomel electrode, and a platinum sheet, respectively. The obtained nickel-cobalt hydroxide composite black phosphorus nanosheet powder was rinsed several times with distilled water and dried in a vacuum oven at 60°C for 4 h.
[0043] (2) Preparation of conductive adhesive: 100 mg of carbon nanotubes and 50 mg of sericin were added to 20 mL of deionized water to prepare a conductive slurry. The mixture was then ultrasonicated for 30 minutes using an ultrasonicator.
[0044] (3) Fabric surface cleaning: Use a mixed solution of deionized water and ethanol in a volume ratio of 1:1 to ultrasonically remove particulate impurities and grease on the fabric surface. After washing with deionized water, dry it in a vacuum oven at 40°C for 6 hours to obtain a fabric substrate with a clean surface.
[0045] (4) Loading of active materials: The conductive adhesive in (2) was vacuum filtered onto a silk fabric (1×1 cm 2 ) surface is covered to obtain a conductive silk fabric, and then nickel cobalt hydroxide composite black phosphorus nanosheets are loaded on the highly conductive silk fabric by vacuum filtration.
[0046] (5) Electrochemical performance test: The nickel cobalt hydroxide composite black phosphorus-based fabric obtained in (4) was subjected to cyclic voltammetry, chronopotentiometry, and AC impedance spectroscopy to explore the electrochemical properties of the obtained fabric.
[0047] Example 4
[0048] (1) Preparation of active material: The electrolyte was prepared by dissolving 1.2 mmol of Ni(NO₃)₂·6H₂O and 1 mmol of Co(NO₃)₂·6H₂O in 100 mL of deionized water. A three-electrode system was used with a potentiostatic method at -10 V for 3000 s. The working electrode, reference electrode, and counter electrode were black phosphorus, a saturated calomel electrode, and a platinum sheet, respectively. The resulting nickel-cobalt hydroxide composite black phosphorus nanosheet powder was rinsed several times with distilled water and dried in a vacuum oven at 60°C for 4 h.
[0049] (2) Preparation of conductive adhesive: 100 mg of carbon nanotubes and 50 mg of sericin were added to 20 mL of deionized water to prepare a conductive slurry. The mixture was then ultrasonicated for 30 minutes using an ultrasonicator.
[0050] (3) Fabric surface cleaning: Use a mixed solution of deionized water and ethanol in a volume ratio of 1:1 to ultrasonically remove particulate impurities and grease on the fabric surface. After washing with deionized water, dry it in a vacuum oven at 40°C for 6 hours to obtain a fabric substrate with a clean surface.
[0051] (4) Loading of active materials: The conductive adhesive in (2) was vacuum filtered onto a silk fabric (1×1 cm 2 ) surface is covered to obtain a conductive silk fabric, and then nickel cobalt hydroxide composite black phosphorus nanosheets are loaded on the highly conductive silk fabric by vacuum filtration.
[0052] (5) Electrochemical performance test: The nickel cobalt hydroxide composite black phosphorus modified silk fabric obtained in (4) was subjected to cyclic voltammetry, chronopotentiometry, and AC impedance spectroscopy to explore the electrochemical properties of the obtained fabric.
[0053] The above-mentioned specific implementation methods are used to illustrate the present invention and are only preferred embodiments of the present invention, rather than limiting the present invention. Any modifications, equivalent substitutions, improvements, etc. made to the present invention within the spirit of the present invention and the scope of protection of the claims shall fall within the scope of protection of the present invention.
Claims
1. A silk-based flexible energy storage fabric, wherein the fabric is a silk fabric or a mixed fabric containing silk, characterized in that: The fabric has a structure in which nickel cobalt hydroxide composite black phosphorus nanosheets are wrapped; the black phosphorus presents a nanosheet structure with 1 to 10 layers, and nickel cobalt hydroxide grows on the nanosheets in the form of particles, wherein the nickel cobalt hydroxide composite black phosphorus nanosheets are loaded on the fabric by reconstructing silk sericin.
2. The nickel-cobalt hydroxide composite black phosphorus-based fabric according to claim 1, characterized in that: The thickness of the fabric is 0.5-5 mm, and the fabric structure is silk woven fabric and knitted fabric.
3. The method for preparing the silk-based flexible energy storage fabric according to claim 1 or 2, characterized in that: The specific steps include: (1) Preparation of active material: nickel source and cobalt source are dissolved in a polar solvent, and black phosphorus is electrochemically stripped using an electrochemical workstation, where black phosphorus is used as the working electrode to obtain nickel-cobalt hydroxide composite black phosphorus nanosheets; (2) Preparation of conductive adhesive: Silk sericin is used as the adhesive and carbon nanotubes as the conductive agent, and the two are mixed by ultrasonic crushing to prepare a highly conductive adhesive slurry; (3) Fabric surface cleaning: The fabric material was immersed in deionized water and ethanol for ultrasonic cleaning to remove surface impurities and grease, and then vacuum dried for loading active materials; (4) Loading of active materials: The conductive adhesive obtained in step (2) is loaded on the fabric by vacuum filtration to form a highly conductive fabric, and then nickel cobalt hydroxide composite black phosphorus nanosheets are loaded on the highly conductive fabric by vacuum filtration to complete the loading of the active materials.
4. The preparation method according to claim 3, characterized in that Nickel sources include nickel chloride, nickel nitrate, and nickel sulfate; cobalt sources include cobalt chloride, cobalt nitrate, and cobalt sulfate; and solvents for dissolving the nickel and cobalt sources include deionized water, formamide, ethanol, glycerol, and propylene glycol.
5. The preparation method according to claim 3, characterized in that The method for electrochemical stripping of black phosphorus using an electrochemical workstation is a constant potential method of the electrochemical workstation, with a voltage set to -4 to -25 volts and a duration of 100 to 20,000 seconds.
6. The preparation method according to claim 3, characterized in that In the step (2), the ultrasonic power is set to 10-50%, and the ultrasonic time is set to 10-120 minutes.
7. The preparation method according to claim 3, characterized in that In step (4), the filtration time is 10 to 20 minutes.
8. The preparation method according to claim 3, characterized in that The concentration range of the added nickel source is 1mmol / L to 1mol / L, and the concentration range of the added cobalt source is 1mmol / L to 1mol / L.
9. The preparation method according to claim 3, characterized in that The mass ratio of sericin to carbon nanotubes is 1:10 to 10:
1.
10. The preparation method according to claim 3, characterized in that The loading amount of the adhesive prepared by sericin and carbon nanotubes on the fabric surface is 1 mg cm -2 ~100mg cm -2 The loading amount of nickel cobalt hydroxide composite black phosphorus nanosheets on the fabric is 1 mg cm -2 ~100mg cm -2 .