Preparation method and application of high-activity ordered conductive fiber

Abstract

The invention provides a preparation method and application of high-activity ordered conductive fibers. MXene is prepared by selectively etching an aluminum atomic layer from a Ti3AlC2MAX phase, MXene fibers are prepared by utilizing wet spinning microflow control, and NiCoMoS polymetallic sulfide nanosheets grow on the MXene fibers. The NiCoMoS-MXene composite conductive fiber prepared by a mode of growing NiCoMoS multi-metal sulfide on the MXene fiber in situ has abundant redox sites, a relatively large specific surface area and relatively high OH <-> adsorption energy, and has high-activity charge transfer and storage redox activity, and the conductivity and the antistatic property of the fiber are remarkably improved. The conductive fiber designed by the invention has a relatively great application prospect in the aspects of batteries, supercapacitors, wearable strain sensors and the like, and can be applied to multiple fields as an intelligent material.

Description

Technical Field

[0001] The invention belongs to the field of conductive fiber materials, and particularly relates to a method for preparing highly active ordered conductive fibers. Background Art

[0002] In recent years, the emerging two-dimensional material MXenes has anisotropic main chains, ordered channels, large specific surface area and high electrochemical activity, and has become one of the best candidate materials for the preparation of highly conductive fibers. The prepared fibers have good high conductivity, high flexibility and light weight. In particular, the ability to control chemical reactions on two-dimensional sheets can highly guarantee directional microstructures and complex functions, thereby improving ion kinetic diffusion and charge storage quality. At the same time, transition metal sulfides (TMSs) are considered to be a new type of pseudo-capacitive electrode / electrode material to replace metal oxides and hydroxides due to their high conductivity, excellent redox reversibility, low electronegativity, high stability and high catalytic activity. Among them, Co3S4 and Ni3S4 have been widely studied as low-cost, highly catalytically active electroactive materials.

[0003] With the continuous research and development and innovation of smart textiles, their excellent and unique properties have brought great convenience to people's lives. One of the main materials for preparing smart textiles is conductive fiber. The research and development of conductive fibers has received great attention from the materials field at home and abroad, and has made good progress in the application areas of electric heating products, nanogenerators, sensors and capacitors. It will surely gain an increasingly important position in the field of materials. The existing conductive fibers currently have problems such as low conductive agent loading, uneven distribution, poor interfacial compatibility and discontinuous conductive networks, resulting in poor conductivity of the prepared conductive composite fibers. This is mainly because the addition of a small amount of conductive agent is not conducive to the construction of a conductive network. The conductive network structure of the fiber is not well connected, and there will be defects in the formation of a conductive path, resulting in poor conductivity. However, if too much conductive agent is added, the spinnability of the mixed spinning solution will be significantly affected. Therefore, it is crucial to prepare a highly active and ordered conductive fiber to effectively construct a complete conductive network to meet the requirements of industrial production. Summary of the Invention

[0004] The purpose of the present invention is to prepare a highly active ordered conductive fiber, increase the strength of the fiber, and improve the conductivity. To this end, the present invention adopts the following technical solutions:

[0005] A method for preparing highly active ordered NiCoMoS-MXene composite conductive fibers, characterized in that the composite electrode is uniformly grown on the MXene surface by a confined assembly technique, comprising the following steps:

[0006] (1) MXene fibers prepared by wet spinning microfluidics;

[0007] (2) NiCoMoS multi-metal sulfide nanosheets were grown on MXene fibers to prepare highly active ordered NiCoMoS-MXene composite conductive fibers.

[0008] According to the technical solution provided by the present invention, the conductive fiber prepared is characterized in that: the MXene includes Ti2CT x , TiNbCT x , Ti3CN x T x ,Ta4C3T x , Nb2CT x , V2CT x , Nb4C3T x , Mo2CT x ; The resistivity of conductive fiber is ≤10 8 Ω / cm; the electrical resistance of the conductive fiber is less than 15Ω; the breaking strength is more than 15cN / dtex; it can be made into slender and soft fibers, with the longest length reaching about 100cm; the diameter of the conductive fiber is 100μm; the color of the conductive fiber is black, and it can bear a weight of about 20g.

[0009] Furthermore, the preparation method comprises the following specific steps:

[0010] (1) Synthesis of MXene: MXene was prepared by selectively etching the aluminum atomic layer from the Ti3AlC2 MAX phase. First, 2 g of lithium fluoride was dissolved in 40 mL of 9 M hydrochloric acid and stirred for 0.5 h to form HF. Then, 2 g of the Ti3AlC2 MAX phase was carefully added to the HF solution and stirred continuously at 37 °C for 48 h. The obtained acidic dispersion was washed with deionized water and centrifuged (3500 rpm, 5 min) until the supernatant was clear. Finally, a MXene colloidal solution was obtained.

[0011] (2) Microfluidic wet spinning of MXene fibers: First, 5 mL of MXene was used with a concentration of 15 mg L -1 The MXene colloidal solution was used as the spinning solution; 4 g of magnesium sulfate, 2 mL of ethanol, and 500 mL of deionized water were used to prepare the coagulation bath. The spinning solution was transferred to a 10 mL plastic syringe with a 19G needle and the spinning solution was pumped at 70 mL h -1 The MXene fibers were extruded into a coagulation bath at a constant rate. The MXene fibers were then coagulated and collected in a magnesium sulfate aqueous solution. Finally, the MXene fibers were dried under natural conditions.

[0012] (3) Preparation of MXene-NiCoMoS highly active ordered fibers (NiCoMoS-MXene): MXene fibers were pretreated with 3M hydrochloric acid, acetone, ethanol, and deionized water to remove unwanted organic impurities. Then, 1 mmol nickel nitrate hexahydrate (Ni(NO3)2·6H2O), 1 mmol cobalt nitrate solution (Co(NO3)2), 1 mmol sodium molybdate dihydrate (Na2MoO4), 300 mg urea, and 74 mg ammonium fluoride (NH4F) were dissolved in 50 mL deionized water and stirred for 20 min. The solution was then ultrasonically treated for 30 min to remove oxygen from the solution to prevent MXene from being oxidized to titanium dioxide. The solution was then vacuum-treated to further remove oxygen. The solution and MXene fibers were subsequently transferred to a 50 mL reactor. The reactor was then sealed and maintained at 150°C for 6 h. After the reaction was completed, the resulting MXene-NiCoMo hydroxide fibers were immersed in deionized water for mild ultrasonic treatment to remove the overgrown polymetallic hydroxides (LDHs) on the surface. The resulting NiCoMo LDHs fibers were dried in a vacuum oven at 60°C for 1 hour. The MXene-NiCoMo LDH fibers were then immersed in an autoclave containing 50 ml of a 0.1 M sodium sulfide aqueous solution. The reaction was carried out at 120°C for 10 hours, followed by washing with deionized water and anhydrous ethanol and mild sonication. Finally, the fibers were dried in a vacuum oven at 60°C for 1 hour. The resulting conductive fibers were designated NiCoMoS-MXene composite conductive fibers.

[0013] In the present invention, unless otherwise specified, the materials used are conventional commercially available products in this field.

[0014] This invention achieves NiCoMoS-MXene composite conductive fibers by in-situ growing NiCoMoS multinary metal sulfide nanosheets on MXene fibers. These fibers exhibit high capacity, strong conductivity, and excellent mechanical properties. The highly active, ordered NiCoMoS-MXene composite conductive fibers obtained through in-situ growth are simple to prepare and readily scalable, demonstrating their potential for applications in smart clothing, medical devices, electronic equipment, and other fields. BRIEF DESCRIPTION OF THE DRAWINGS

[0015] Figure 1 SEM image of a highly active ordered NiCoMoS-MXene composite conductive fiber provided as an example of the present invention. The left side is an SEM image of the NiCoMoS-MXene-2 ​​surface, and the right side is an SEM image of the NiCoMoS-MXene-2 ​​cross-section.

[0016] Figure 2 The conductive properties of the composite fibers prepared with different NiCoMoS loadings in different examples. DETAILED DESCRIPTION

[0017] The following is an explanation of the embodiments of the present invention: This embodiment is implemented under the premise of the technical solution of the present invention, and provides a detailed implementation method and operation process, but the scope of protection of the present invention is not limited to the following embodiments. The following is a further detailed explanation of the preparation method of a highly active ordered MXene composite conductive fiber provided by the present invention using MXene as an example, wherein X is the surface end group of MXene (such as fluorine, hydroxyl, etc.)

[0018] Example 1:

[0019] (1) Synthesis of MXene: MXene was prepared by selectively etching the aluminum atomic layer from the Ti3AlC2 MAX phase. First, 2 g of lithium fluoride was dissolved in 40 mL of 9 M hydrochloric acid and stirred for 0.5 h to form HF. Then, 2 g of the Ti3AlC2 MAX phase was carefully added to the HF solution and stirred continuously at 37 °C for 48 h. The obtained acidic dispersion was washed with deionized water and centrifuged (3500 rpm, 5 min) until the supernatant was clear. Finally, a MXene colloidal solution was obtained.

[0020] (2) Microfluidic wet spinning of MXene fibers: First, 5 mL of MXene was used with a concentration of 15 mg L -1 The MXene colloidal solution was used as the spinning solution; 4 g of magnesium sulfate, 2 mL of ethanol, and 500 mL of deionized water were used to prepare the coagulation bath. The spinning solution was transferred to a 10 mL plastic syringe with a 19G needle and the spinning solution was pumped at 70 mL h -1 The MXene fibers were extruded into a coagulation bath at a constant rate. The MXene fibers were then coagulated and collected in a magnesium sulfate aqueous solution. Finally, the MXene fibers were dried under natural conditions.

[0021] (3) Preparation of highly active ordered NiCoMoS-MXene composite conductive fibers: MXene fibers were pretreated with 3M hydrochloric acid, acetone, ethanol, and deionized water to remove unwanted organic impurities. Then, 0.5mmol nickel nitrate hexahydrate (Ni(NO3)2·6H2O), 0.5mmol cobalt nitrate solution (Co(NO3)2), 0.5mmol sodium molybdate dihydrate (Na2MoO4), 150mg urea, and 37mg ammonium fluoride (NH4F) were dissolved in 50mL deionized water and stirred for 20min. The solution was then ultrasonically treated for 30min to remove oxygen from the solution to prevent MXene from being oxidized to titanium dioxide. The solution was then vacuum-treated to further remove oxygen. The solution and MXene fibers were subsequently transferred to a 50mL reactor. The reactor was then sealed and maintained at 150°C for 6h. After the reaction was completed, the resulting MXene-NiCoMo hydroxide fibers were immersed in deionized water for mild ultrasonic treatment to remove the overgrown polymetallic hydroxides (LDHs) on the surface. The resulting NiCoMo LDHs fibers were dried in a vacuum oven at 60°C for 1 hour. The MXene-NiCoMo LDH fibers were then immersed in 50 ml of a 0.05 M sodium sulfide aqueous solution in an autoclave and reacted at 120°C for 10 hours. The fibers were then washed with deionized water and anhydrous ethanol and subjected to a mild ultrasonic treatment. Finally, they were dried in a vacuum oven at 60°C for 1 hour. The resulting conductive fibers were designated NiCoMoS-MXene-1 composite conductive fibers.

[0022] Example 2:

[0023] (1) Synthesis of MXene: MXene was prepared by selectively etching the aluminum atomic layer from the Ti3AlC2 MAX phase. First, 2 g of lithium fluoride was dissolved in 40 mL of 9 M hydrochloric acid and stirred for 0.5 h to form HF. Then, 2 g of the Ti3AlC2 MAX phase was carefully added to the HF solution and stirred continuously at 37 °C for 48 h. The obtained acidic dispersion was washed with deionized water and centrifuged (3500 rpm, 5 min) until the supernatant was clear. Finally, a MXene colloidal solution was obtained.

[0024] (2) Microfluidic wet spinning of MXene fibers: First, 5 mL of MXene was used with a concentration of 15 mg L -1 The MXene colloidal solution was used as the spinning solution; 4 g of magnesium sulfate, 2 mL of ethanol, and 500 mL of deionized water were used to prepare the coagulation bath. The spinning solution was transferred to a 10 mL plastic syringe with a 19G needle and the spinning solution was pumped at 70 mL h -1 The MXene fibers were extruded into a coagulation bath at a constant rate. The MXene fibers were then coagulated and collected in a magnesium sulfate aqueous solution. Finally, the MXene fibers were dried under natural conditions.

[0025] (3) Preparation of highly active ordered NiCoMoS-MXene composite conductive fibers: MXene fibers were pretreated with 3M hydrochloric acid, acetone, ethanol, and deionized water to remove unwanted organic impurities. Then, 1mmol nickel nitrate hexahydrate (Ni(NO3)2·6H2O), 1mmol cobalt nitrate solution (Co(NO3)2), 1mmol sodium molybdate dihydrate (Na2MoO4), 300mg urea, and 74mg ammonium fluoride (NH4F) were dissolved in 50mL deionized water and stirred for 20min. The solution was then ultrasonically treated for 30min to remove oxygen from the solution to prevent MXene from being oxidized to titanium dioxide. The solution was then vacuum-treated to further remove oxygen. The solution and MXene fibers were subsequently transferred to a 50mL reactor. The reactor was then sealed and maintained at 150°C for 6h. After the reaction was completed, the resulting MXene-NiCoMo hydroxide fibers were immersed in deionized water for mild ultrasonic treatment to remove the overgrown polymetallic hydroxides (LDHs) on the surface. The resulting NiCoMo LDHs fibers were dried in a vacuum oven at 60°C for 1 hour. The MXene-NiCoMo LDH fibers were then immersed in 50 ml of 0.1 M sodium sulfide aqueous solution in an autoclave and reacted at 120°C for 10 hours. The fibers were then washed with deionized water and anhydrous ethanol and subjected to a mild ultrasonic treatment. Finally, they were dried in a vacuum oven at 60°C for 1 hour. The resulting conductive fibers are designated NiCoMoS-MXene-2 ​​composite conductive fibers.

[0026] Example 3:

[0027] (1) Synthesis of MXene: MXene was prepared by selectively etching the aluminum atomic layer from the Ti3AlC2 MAX phase. First, 2 g of lithium fluoride was dissolved in 40 mL of 9 M hydrochloric acid and stirred for 0.5 h to form HF. Then, 2 g of the Ti3AlC2 MAX phase was carefully added to the HF solution and stirred continuously at 37 °C for 48 h. The obtained acidic dispersion was washed with deionized water and centrifuged (3500 rpm, 5 min) until the supernatant was clear. Finally, a MXene colloidal solution was obtained.

[0028] (2) Microfluidic wet spinning of MXene fibers: First, 5 mL of MXene was used with a concentration of 15 mg L -1 The MXene colloidal solution was used as the spinning solution; 4 g of magnesium sulfate, 2 mL of ethanol, and 500 mL of deionized water were used to prepare the coagulation bath. The spinning solution was transferred to a 10 mL plastic syringe with a 19G needle and the spinning solution was pumped at 70 mL h -1 The MXene fibers were extruded into a coagulation bath at a constant rate. The MXene fibers were then coagulated and collected in a magnesium sulfate aqueous solution. Finally, the MXene fibers were dried under natural conditions.

[0029] (3) Preparation of highly active ordered NiCoMoS-MXene composite conductive fibers: MXene fibers were pretreated with 3M hydrochloric acid, acetone, ethanol, and deionized water to remove unwanted organic impurities. Then, 1.5mmol nickel nitrate hexahydrate (Ni(NO3)2·6H2O), 1.5mmol cobalt nitrate solution (Co(NO3)2), 1.5mmol sodium molybdate dihydrate (Na2MoO4), 450mg urea, and 111mg ammonium fluoride (NH4F) were dissolved in 50mL deionized water and stirred for 20min. The solution was then ultrasonically treated for 30min to remove oxygen from the solution to prevent MXene from being oxidized to titanium dioxide. The solution was then vacuum-treated to further remove oxygen. The solution and MXene fibers were subsequently transferred to a 50mL reactor. The reactor was then sealed and maintained at 150°C for 6h. After the reaction was completed, the resulting MXene-NiCoMo hydroxide fibers were immersed in deionized water for mild ultrasonic treatment to remove the overgrown polymetallic hydroxides (LDHs) on the surface. The resulting NiCoMo LDHs fibers were dried in a vacuum oven at 60°C for 1 hour. The MXene-NiCoMo LDH fibers were then immersed in an autoclave containing 50 ml of a 0.15 M sodium sulfide aqueous solution and reacted at 120°C for 10 hours. The fibers were then washed with deionized water and anhydrous ethanol and subjected to a mild sonication treatment. Finally, they were dried in a vacuum oven at 60°C for 1 hour. The resulting conductive fibers are designated NiCoMoS-MXene-3 composite conductive fibers.

[0030] Example 4:

[0031] (1) Synthesis of MXene: MXene was prepared by selectively etching the aluminum atomic layer from the Ti3AlC2 MAX phase. First, 2 g of lithium fluoride was dissolved in 40 mL of 9 M hydrochloric acid and stirred for 0.5 h to form HF. Then, 2 g of the Ti3AlC2 MAX phase was carefully added to the HF solution and stirred continuously at 37 °C for 48 h. The obtained acidic dispersion was washed with deionized water and centrifuged (3500 rpm, 5 min) until the supernatant was clear. Finally, a MXene colloidal solution was obtained.

[0032] (2) Microfluidic wet spinning of MXene fibers: First, 5 mL of MXene was used with a concentration of 15 mg L -1 The MXene colloidal solution was used as the spinning solution; 4 g of magnesium sulfate, 2 mL of ethanol, and 500 mL of deionized water were used to prepare the coagulation bath. The spinning solution was transferred to a 10 mL plastic syringe with a 19G needle and the spinning solution was pumped at 70 mL h -1The MXene fibers were extruded into a coagulation bath at a constant rate. The MXene fibers were then coagulated and collected in a magnesium sulfate aqueous solution. Finally, the MXene fibers were dried under natural conditions.

[0033] (3) Preparation of highly active ordered NiCoMoS-MXene composite conductive fibers: MXene fibers were pretreated with 3M hydrochloric acid, acetone, ethanol, and deionized water to remove unwanted organic impurities. Then, 2mmol nickel nitrate hexahydrate (Ni(NO3)2·6H2O), 2mmol cobalt nitrate solution (Co(NO3)2), 2mmol sodium molybdate dihydrate (Na2MoO4), 600mg urea, and 148mg ammonium fluoride (NH4F) were dissolved in 50mL deionized water and stirred for 20min. The solution was then ultrasonically treated for 30min to remove oxygen from the solution to prevent MXene from being oxidized to titanium dioxide. The solution was then vacuum-treated to further remove oxygen. The solution and MXene fibers were subsequently transferred to a 50mL reactor. The reactor was then sealed and maintained at 150°C for 6h. After the reaction was completed, the resulting MXene-NiCoMo hydroxide fibers were immersed in deionized water for mild ultrasonic treatment to remove the overgrown polymetallic hydroxides (LDHs) on the surface. The resulting NiCoMo LDHs fibers were dried in a vacuum oven at 60°C for 1 hour. The MXene-NiCoMo LDH fibers were then immersed in 50 ml of a 0.2 M sodium sulfide aqueous solution in an autoclave and reacted at 120°C for 10 hours. The fibers were then washed with deionized water and anhydrous ethanol and subjected to a mild ultrasonic treatment. Finally, they were dried in a vacuum oven at 60°C for 1 hour. The resulting conductive fibers are designated NiCoMoS-MXene-4 composite conductive fibers.

[0034] In the present invention, the highly active ordered NiCoMoS-MXene composite conductive fiber obtained has good electrical conductivity and antistatic properties. By regulating the growth time of the multi-metal sulfide, NiCoMoS-MXene composite conductive fibers with different specific surface areas and electrical conductivity are obtained, achieving high capacity, high conductivity and good mechanical properties. The NiCoMoS-MXene composite conductive fiber obtained by in situ growth is simple to prepare, easy to achieve large-scale production, and has great application potential in flame retardancy and antistatic properties. Figure 1 As shown in FIG, the SEM image of the NiCoMoS-MXene-2 ​​composite fiber prepared in Example 2 has a three-dimensional wrinkled structure. The fiber has high electrochemical activity and good conductivity. Figure 2 As shown, the conductive properties of NiCoMoS-MXene-1, NiCoMoS-MXene-2, NiCoMoS-MXene-3 and NiCoMoS-MXene-4 composite fibers are demonstrated.

[0035] 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 method for preparing ordered NiCoMoS-MXene composite conductive fibers, characterized in that: The composite electrode is produced by a confined assembly technique, so that polymetallic sulfides are uniformly grown on the surface of MXene. The preparation method comprises the following steps: (1) MXene fibers prepared by wet spinning microfluidics; (2) NiCoMoS multi-metal sulfide nanosheets were grown on MXene fibers to prepare highly active ordered NiCoMoS-MXene composite conductive fibers.

2. The method for preparing conductive fiber according to claim 1, characterized in that: The MXene includes Ti2CT x , TiNbCT x , Ti3CN x T x ,Ta4C3T x , Nb2CT x , V2CT x , Nb4C3T x , Mo2CT x .

3. The method for preparing conductive fiber according to claim 1, wherein: The resistance of the conductive fiber is less than 15Ω, and the resistivity is ≤10 8 Ω / cm.

4. The method for preparing conductive fiber according to claim 1, wherein: The conductive fiber has a breaking strength of 15 cN / dtex or more.

5. The method for preparing conductive fiber according to claim 1, characterized in that: The conductive fiber has a diameter of 100 μm.

6. The method for preparing conductive fiber according to claim 1, characterized in that: The conductive fiber can be made into a slender and flexible fiber, with a maximum length of up to 100 cm.

7. The method for preparing conductive fiber according to claim 1, characterized in that: The conductive fiber is black in color and can bear a weight of about 20g.

8. The method for preparing the conductive fiber according to claim 1, comprising the following specific steps: (1) Preparation of MXene by selectively etching the aluminum atomic layer from the Ti3AlC2 MAX phase: First, 2 g of lithium fluoride was dissolved in 40 mL of 9 M hydrochloric acid and stirred for 0.5 h to form HF. Then, 2 g of the Ti3AlC2 MAX phase was carefully added to the HF solution and stirred continuously at 37 °C for 48 h. The obtained dispersion was washed with deionized water and centrifuged at 3500 rpm until the supernatant was clear. Finally, a MXene colloidal solution was obtained. (2) Microfluidic wet spinning of MXene fibers: First, 5 mL of MXene was used with a concentration of 15 mg L -1 The MXene colloidal solution was used as the spinning solution; 4 g of magnesium sulfate, 2 mL of ethanol, and 500 mL of deionized water were used to prepare the coagulation bath; the spinning solution was transferred to a 10 mL plastic syringe with a 19G needle and the spinning solution was pumped at 70 mL h -1 The MXene fibers were extruded into a coagulation bath at a constant rate; subsequently, the MXene fibers were coagulated and collected in a magnesium sulfate aqueous solution; finally, the MXene fibers were dried under natural conditions; (3) Preparation of highly active ordered NiCoMoS-MXene composite conductive fibers: MXene fibers were pretreated with 3M hydrochloric acid, acetone, ethanol and deionized water to remove unwanted organic impurities; then, 1mmol nickel nitrate hexahydrate, 1mmol cobalt nitrate solution, 1mmol sodium molybdate dihydrate, 300mg urea and 74mg ammonium fluoride were dissolved in 50mL deionized water and stirred for 20min; then ultrasonic treatment was performed for 30min to remove oxygen in the solution to prevent MXene from being oxidized to titanium dioxide; then vacuum treatment was performed on the solution to further remove oxygen; then the solution and MXene fibers were transferred to a 50mL reactor; then, the reactor was sealed and kept at 150℃ for 6h; after the reaction was completed, the generated MXene-NiCoMo hydroxide fibers were immersed in deionized water for mild ultrasonic treatment to remove the overgrown polymetallic hydroxides on the surface; the obtained NiCoMo LDHs fibers were dried in a vacuum oven at 60℃ for 1h; then, the MXene-NiCoMo The LDH fibers were immersed in a high-pressure reactor containing a 0.2 M sodium sulfide aqueous solution; the reaction was carried out at 120°C for 10 h, followed by washing with deionized water and anhydrous ethanol and slight ultrasonic treatment; finally, they were dried in a vacuum oven at 60°C for 1 h; the resulting conductive fibers were designated as NiCoMoS-MXene composite conductive fibers.

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