CN112331378B - Flexible wearable conductive material with Joule heating performance and preparation method thereof - Google Patents

Flexible wearable conductive material with Joule heating performance and preparation method thereof Download PDF

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CN112331378B
CN112331378B CN202011305413.2A CN202011305413A CN112331378B CN 112331378 B CN112331378 B CN 112331378B CN 202011305413 A CN202011305413 A CN 202011305413A CN 112331378 B CN112331378 B CN 112331378B
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nickel
carbon fiber
fabric
tungsten
flexible
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CN112331378A (en
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秦风
白宇
吕银祥
严志洋
高原
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Institute of Applied Electronics of CAEP
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
    • H01B1/14—Conductive material dispersed in non-conductive inorganic material
    • H01B1/16—Conductive material dispersed in non-conductive inorganic material the conductive material comprising metals or alloys
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
    • D06M11/83—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with metals; with metal-generating compounds, e.g. metal carbonyls; Reduction of metal compounds on textiles
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M2101/00—Chemical constitution of the fibres, threads, yarns, fabrics or fibrous goods made from such materials, to be treated
    • D06M2101/40—Fibres of carbon

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  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Chemical & Material Sciences (AREA)
  • Dispersion Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Chemically Coating (AREA)
  • Chemical Or Physical Treatment Of Fibers (AREA)

Abstract

The invention particularly relates to a flexible wearable conductive material with joule heating performance and a preparation method thereof. The material takes flexible carbon fiber as a substrate, and a nickel-tungsten-phosphorus ternary alloy conductive coating is arranged on the surface of the flexible carbon fiber. The preparation method of the flexible carbon fiber substrate surface with the nickel-tungsten-phosphorus ternary alloy conductive coating comprises the following steps: sequentially placing the carbon fiber fabric in ethanol and deionized water for ultrasonic cleaning, and then rinsing and drying the carbon fiber fabric; the carbon fiber substrate is subjected to surface treatment by adopting a KH550 silane coupling agent solution; the nickel nano particles are formed by reducing nickel ions by a sodium borohydride solution; and soaking the carbon fiber fabric activated by the nickel nano particles into Ni-W-P chemical plating solution, washing with deionized water after chemical plating, and drying to obtain the Ni-W-P ternary alloy coated carbon fiber fabric. The material has simple preparation conditions, low cost and strong operability; the prepared novel flexible wearable conductive material has good conductivity and excellent Joule heating performance.

Description

Flexible wearable conductive material with Joule heating performance and preparation method thereof
Technical Field
The invention belongs to the technical field of wearable electronic materials, and particularly relates to a flexible wearable conductive material with joule heating performance and a preparation method thereof.
Background
The flexible wearable conductive material is formed by bonding a flexible insulating material surface such as polyester, polyamide, carbon fiber or PET and the like with a specific conductive material through certain process treatment, has wide application in the directions of wearable shielding materials, wearable electronic devices, sensors and the like, and is one of the research fields of the modern science and technology hotspots. With the vigorous development of scientific technology, the working environment of wearable equipment is gradually complicated, and the working reliability of the wearable equipment in extremely cold environments such as polar regions and outer space is not well guaranteed at present. Therefore, it is necessary to develop a conductive material that can achieve temperature stability by controlling joule heating performance so as to meet the application requirements of wearable electronic technology under extreme cold conditions.
In recent years, the related art invention has also received sufficient attention. Conductive polymers are commonly used as fillers for blending with other polymers due to their light weight and chemical stability characteristics; however, in the case of a high content of conductive polymer, it is difficult to avoid the decrease of the conductive performance and the mechanical performance of the composite material caused by the random distribution of the conductive polymer, which is not favorable for the application in daily life. Due to the large surface area and mechanical flexibility, the reduced graphene oxide (rGO) sheet is also used for preparing a flexible wearable conductive material, but the complex deposition and reduction processes of the sheet greatly increase the preparation cost and limit the heating temperature range. Metals have attracted attention in recent years for flexible wearable conductive materials due to their advantages of excellent conductivity, ease of handling, and economical and efficient preparation methods. However, the heat generating performance of the metal is limited to some extent due to its property of being too conductive.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and solve the requirements and the problems, and provides a smart technical means for preparing the flexible nickel-tungsten-phosphorus (Ni-W-P) ternary alloy coating-coated carbon fiber fabric. The prepared composite material has excellent conductivity, and meanwhile, due to the introduction of the tungsten element, the impedance of the alloy is effectively adjusted, so that the flexible fabric also has excellent Joule heating performance. And through the multiple cycle experiments of heating and cooling, the heating performance and the efficiency of the heating device are not obviously changed, the stability of the heating performance is proved, and the long-term stable use requirement in industry can be met.
In order to achieve the above purpose, the specific technical scheme of the invention is as follows:
a flexible wearable conductive material with Joule heating performance takes flexible carbon fiber as a substrate, and the surface of the flexible carbon fiber substrate is provided with a conductive coating of a nickel-tungsten-phosphorus (Ni-W-P) ternary alloy; the conductive coating of the Ni-W-P ternary alloy is prepared by an electroless plating mode.
The surface of the flexible carbon fiber substrate is provided with a conductive coating of a nickel-tungsten-phosphorus ternary alloy, which means that the surface alloy of the carbon fiber fabric is metalized, and the specific process comprises the following steps: 1) ultrasonic cleaning of the surface of the carbon fiber substrate; 2) modifying the surface of the carbon fiber matrix by using a KH550 silane coupling agent solution; 3) nickel nano-particle autocatalytic activation and chemical alloy plating, etc.
A preparation method of a flexible nickel-tungsten-phosphorus (Ni-W-P) ternary alloy coating coated carbon fiber fabric specifically comprises the following steps:
step (1): placing the carbon fiber fabric in ethanol and deionized water in sequence, ultrasonically cleaning the surface, rinsing and drying the carbon fiber fabric, and removing grease and impurities;
step (2): soaking the fabric in a KH550 silane coupling agent solution, and then placing the fabric in an oven for drying;
and (3): preliminarily preparing a nickel ion solution, soaking the surface-modified fabric in the nickel ion solution at room temperature, then placing the soaked fabric in a sodium borohydride solution, and finally reducing the nickel ions on the surface of the fabric into nickel nano particles to realize the catalytic activation of the nickel nano particles;
and (4): and immediately immersing the activated carbon fiber fabric into Ni-W-P alloy chemical plating solution after the activation of the nickel nano particles. After removal from the electroless plating solution, the fabric samples were rinsed with deionized water and placed in an oven to facilitate surface drying. Finally, the Ni-W-P ternary alloy coated carbon fiber fabric is successfully prepared.
In a preferred embodiment, in the step (2), a KH550 silane coupling agent solution with a mass concentration of 0.5 to 10% and ethanol as a solvent are used as the modifying solution, mixed, sealed and placed in a cool and dry place for 0.5 to 48 hours, and then used.
In a preferred embodiment, step (3) is performed by autocatalytic activation using nickel nanoparticles.
In a preferred embodiment, in step (3), the nickel ion solution is prepared by dissolving nickel sulfate hexahydrate and sodium hypophosphite in deionized water, wherein: the concentrations of the nickel sulfate hexahydrate and the sodium hypophosphite solution are respectively as follows: 5-50g/L and 5-30 g/L.
As a preferred embodiment, in step (3), the concentration of the sodium borohydride solution is 0.5-8M.
In a preferred embodiment, in the step (4), the concentrations of the solutes in the electroplating solution are respectively as follows: 5-50g/L of nickel sulfate hexahydrate, 5-50g/L of sodium tungstate dihydrate, 10-50g/L of ammonium citrate and 5-30g/L of sodium hypophosphite.
As a preferred embodiment, in the step (4), the pH of the alloy electroless plating solution is 8 to 11.5.
In a preferred embodiment, in the step (4), the electroless plating temperature is 50 to 95 ℃ and the time is 10 to 120 minutes.
The main scheme and the further selection schemes can be freely combined to form a plurality of schemes which are all adopted and claimed by the invention; in the invention, the selection (each non-conflict selection) and other selections can be freely combined. The skilled person in the art can understand that there are many combinations, which are all the technical solutions to be protected by the present invention, according to the prior art and the common general knowledge after understanding the scheme of the present invention, and the technical solutions are not exhaustive herein.
Compared with the prior art, the invention has the beneficial effects that:
according to the invention, the Ni-W-P ternary alloy conductive coating is prepared on the surface of the flexible carbon fiber fabric, so that the material has good flexibility and strong bending performance, and can meet the requirements of wearable materials.
In the preparation process, KH550 silane coupling agent solution is adopted to carry out surface modification on the carbon fiber substrate, more active groups are connected after the surface of the carbon fiber fabric is modified, the adhesion between the conductive coating and the substrate is enhanced, the bonding strength between metal and the fabric can be improved without adhesive, and the problem of substrate damage caused by the traditional organic solvent modification or strong base etching method is avoided.
And (III) the nickel nanoparticles are used as reducing particles, so that the reduction efficiency is higher, and meanwhile, the use of toxic noble metal catalysts such as palladium and the like is avoided, and the subsequent reaction is not polluted.
The heating performance with high repeatability and wide heating range can be realized without adding other fillers except metal, the whole preparation process has simple condition, low cost, convenient operation and energy conservation, and the modification activation and chemical plating mode is used, the condition is mild and the operability is strong; the obtained alloy-coated flexible conductive fabric has good conductivity and excellent Joule heating performance (high heating efficiency and wide heating temperature range).
Drawings
Fig. 1 is a flow chart of the preparation of the novel flexible wearable conductive material.
Fig. 2 is a scanning electron microscope image of the novel flexible wearable conductive material prepared in example 1.
FIG. 3 is a graph showing the Joule heating behavior of the composite material prepared in example 1 under an applied voltage of 1V.
FIG. 4 is a graph showing the Joule heating behavior of the composite material prepared in example 1 under an applied voltage of 1.5V.
FIG. 5 is a graph showing the Joule heating behavior of the composite material prepared in example 1 under a 2V energization voltage.
FIG. 6 is a graph of the multiple cycle Joule heating behavior of the composite material prepared in example 1 under a 2V energization voltage.
Fig. 7 is a scanning electron microscope image of the novel flexible wearable conductive material prepared in example 2.
FIG. 8 is a graph showing the Joule heating behavior of the composite material prepared in example 2 under an applied voltage of 1V.
FIG. 9 is a graph showing the Joule heating behavior of the composite material prepared in example 2 under an applied voltage of 1.5V.
FIG. 10 is a graph showing the Joule heating behavior of the composite material prepared in example 2 under a 2V energization voltage.
FIG. 11 is a graph of the multiple cycle Joule heating behavior of the composite material prepared in example 2 under a 2V energization voltage.
Fig. 12 is a scanning electron microscope image of the novel flexible wearable conductive material prepared in example 3.
FIG. 13 is a graph showing the Joule heating behavior of the composite material prepared in example 3 under an applied voltage of 1V.
FIG. 14 is a graph showing the Joule heating behavior of the composite material prepared in example 3 under a 1.5V energization voltage.
FIG. 15 is a graph showing the Joule heating behavior of the composite material prepared in example 3 under a 2V energization voltage.
FIG. 16 is a graph of the multiple cycle Joule heating performance of the composite material prepared in example 3 under a 2V energization voltage.
FIG. 17 is a graph showing Joule heating behavior under a 5V electrification voltage condition of the composite material prepared in comparative example 1.
Detailed Description
As shown in fig. 1, a flexible wearable conductive material with joule heating performance takes flexible carbon fiber as a substrate, and the surface of the flexible carbon fiber substrate is provided with a conductive coating of nickel-tungsten-phosphorus (Ni-W-P) ternary alloy; the conductive coating of the Ni-W-P ternary alloy is prepared by an electroless plating mode.
The surface of the flexible carbon fiber substrate is provided with a conductive coating of a nickel-tungsten-phosphorus ternary alloy, which means that the surface alloy of the carbon fiber fabric is metalized, and the specific process comprises the following steps: 1) ultrasonic cleaning of the surface of the carbon fiber substrate; 2) modifying the surface of the carbon fiber matrix by using a KH550 silane coupling agent solution; 3) nickel nano-particle autocatalytic activation and chemical alloy plating, etc.
The embodiments of the present invention are described below with reference to specific embodiments, and other advantages and effects of the present invention will be easily understood by those skilled in the art from the disclosure of the present specification. The invention is capable of other and different embodiments and of being practiced or of being carried out in various ways, and its several details are capable of modification in various respects, all without departing from the spirit and scope of the present invention. It is to be noted that the features in the following embodiments and examples may be combined with each other without conflict.
It should be noted that, in order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention are clearly and completely described below, and it is obvious that the described embodiments are some embodiments of the present invention, but not all embodiments.
Thus, the following detailed description of the embodiments of the present invention is not intended to limit the scope of the invention as claimed, but is merely representative of selected embodiments of the invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The% used in the following examples and comparative examples, unless otherwise specified, are expressed in terms of% by mass, i.e., wt%.
Example 1:
a preparation method of a flexible wearable conductive material with Joule heating performance comprises the following steps:
1) ultrasonic cleaning of carbon fiber substrate surface
The carbon fiber fabric is cut into a square with the size of 10cm multiplied by 10cm, the square is sequentially placed in ethanol and deionized water to carry out ultrasonic cleaning on the surface, and then rinsing and drying are carried out on the surface.
2) Modifying the surface of a carbon fiber matrix by using a KH550 silane coupling agent solution
The fabric is soaked in a 3% KH550 solution for 30 minutes, the solvent is ethanol, and then the fabric is dried in an oven at 120 ℃.
3) Autocatalytic activation of nickel nanoparticles
Preliminarily preparing a nickel ion solution, wherein the nickel ion solution is prepared by dissolving nickel sulfate hexahydrate and sodium hypophosphite in deionized water, and the preparation method comprises the following steps: the concentrations of the nickel sulfate hexahydrate solution and the sodium hypophosphite solution are respectively 20g/L and 30 g/L. The surface-modified fabric was immersed in a nickel ion solution at room temperature for 10 minutes.
Then, the soaked fabric is placed in NaBH4The reaction was carried out in solution (0.5M) for 10 minutes. The nickel ions on the surface of the fabric are finally reduced into nickel nano particles to realize the catalytic activity of the nickel nano particlesAnd (4) transforming.
4) Chemical plating of alloys
Immediately after activation of the nickel nanoparticles, the fabric was immersed in 500ml of Ni-W-P alloy electroless plating solution and heated at a constant temperature of 90 ℃ for 40 minutes. The solvent of the Ni-W-P alloy chemical plating solution is deionized water, and the concentrations of various solutes in the solution are respectively as follows: 20g/L of nickel sulfate hexahydrate, 5g/L of sodium tungstate dihydrate, 15g/L of ammonium citrate, 15g/L of sodium hypophosphite and a pH value of 10. After removal from the electroless plating solution, the fabric samples were rinsed with deionized water and placed in a 60 ℃ oven to facilitate surface drying. Finally, the carbon fiber fabric coated with the Ni-W-P ternary alloy is obtained.
Scanning the prepared flexible wearable conductive material by an electron microscope, as shown in fig. 2, fig. 2 is a scanning electron microscope image of the novel flexible wearable conductive material prepared in this embodiment.
FIGS. 3 to 5 are graphs of Joule heating behavior of the composite material prepared in example 1 at different applied voltages, and experiments show that the composite material can reach a heating temperature of 44 ℃ within 60s under the condition of 1V applied voltage; under the condition of 1.5V electrifying voltage, the heating temperature of 62 ℃ can be reached within 60 s; under the condition of 2V electrifying voltage, the heating temperature of 123 ℃ can be reached within 45s, and the composite material is proved to have excellent heating efficiency and joule heating temperature range. FIG. 6 is a graph of multiple cycle Joule heating behavior of the composite material prepared in example 1 under a 2V energization voltage, with experimental results showing that: after the composite material is subjected to single, 20 and 50 times of cyclic heating, the heating performance and efficiency of the composite material are not greatly changed, and the heating stability of the composite material is proved. The conductivity of the composite material was measured with a conductivity meter (Lei Chen instrument, model DDS-307) to obtain a conductivity of 4.15 × 103S/m shows that the prepared flexible wearable conductive material has good conductive performance.
Example 2:
a preparation method of a flexible wearable conductive material with Joule heating performance comprises the following steps:
1) ultrasonic cleaning of carbon fiber substrate surface
The carbon fiber fabric is cut into a square with the size of 10cm multiplied by 10cm, the square is sequentially placed in ethanol and deionized water to carry out ultrasonic cleaning on the surface, and then rinsing and drying are carried out on the surface.
2) Modifying the surface of a carbon fiber matrix by using a KH550 silane coupling agent solution
The fabric is soaked in a 3% KH550 solution for 30 minutes, the solvent is ethanol, and then the fabric is dried in an oven at 120 ℃.
3) Autocatalytic activation of nickel nanoparticles
Preliminarily preparing a nickel ion solution, wherein the nickel ion solution is prepared by dissolving nickel sulfate hexahydrate and sodium hypophosphite in deionized water, and the preparation method comprises the following steps: the concentrations of the nickel sulfate hexahydrate solution and the sodium hypophosphite solution are respectively 30g/L and 20 g/L. The surface-modified fabric was immersed in a nickel ion solution at room temperature for 10 minutes.
Then, the soaked fabric is placed in NaBH4The reaction was carried out in solution (4M) for 10 minutes. The nickel ions on the surface of the fabric are finally reduced into nickel nano particles, so that the catalytic activation of the nickel nano particles is realized.
4) Chemical plating of alloys
Immediately after activation of the nickel nanoparticles, the fabric was immersed in 500ml of Ni-W-P alloy electroless plating solution and heated at a constant temperature of 60 ℃ for 100 minutes. The solvent of the Ni-W-P alloy chemical plating solution is deionized water, and the concentrations of various solutes in the solution are respectively as follows: 25g/L of nickel sulfate hexahydrate, 10g/L of sodium tungstate dihydrate, 25g/L of ammonium citrate, 30g/L of sodium hypophosphite and the pH value of 11. After removal from the electroless plating solution, the fabric samples were rinsed with deionized water and placed in a 70 ℃ oven to facilitate surface drying. Finally, the carbon fiber fabric coated with the Ni-W-P ternary alloy is obtained.
Scanning the prepared flexible wearable conductive material by an electron microscope, as shown in fig. 7, fig. 7 is a scanning electron microscope image of the novel flexible wearable conductive material prepared in this embodiment.
FIGS. 8 to 10 are graphs of Joule heating behavior of the composite material prepared in example 2 under different applied voltages, and experiments show that the composite material can reach a heating temperature of 43 ℃ within 60s under the condition of 1V applied voltage; under the condition of 1.5V of electrifying voltage, the voltage can be adjustedThe exothermic temperature of 58 ℃ is reached within 60 s; under the condition of 2V electrifying voltage, the heating temperature of 118 ℃ can be reached within 60s, and the composite material is proved to have excellent heating efficiency and joule heating temperature range. FIG. 11 is a graph of multiple cycle Joule heating behavior of the composite material prepared in example 2 under a 2V energization voltage, with experimental results showing: after the composite material is subjected to single, 20 and 50 times of cyclic heating, the heating performance and efficiency of the composite material are not greatly changed, and the heating stability of the composite material is proved. The conductivity of the composite material was measured with a conductivity meter (Lei Chen instrument, model DDS-307) to obtain a conductivity of 4.21 × 103S/m shows that the prepared flexible wearable conductive material has good conductive performance.
Example 3:
a preparation method of a flexible wearable conductive material with Joule heating performance comprises the following steps:
1) ultrasonic cleaning of carbon fiber substrate surface
The carbon fiber fabric is cut into a square with the size of 10cm multiplied by 10cm, the square is sequentially placed in ethanol and deionized water to carry out ultrasonic cleaning on the surface, and then rinsing and drying are carried out on the surface.
2) Modifying the surface of a carbon fiber matrix by using a KH550 silane coupling agent solution
The fabric is soaked in a 3% KH550 solution for 30 minutes, the solvent is ethanol, and then the fabric is dried in an oven at 120 ℃.
3) Autocatalytic activation of nickel nanoparticles
Preliminarily preparing a nickel ion solution, wherein the nickel ion solution is prepared by dissolving nickel sulfate hexahydrate and sodium hypophosphite in deionized water, and the preparation method comprises the following steps: the concentrations of the nickel sulfate hexahydrate and the sodium hypophosphite solution are respectively 10g/L and 10 g/L. The surface-modified fabric was immersed in a nickel ion solution at room temperature for 10 minutes.
Then, the soaked fabric is placed in NaBH4The reaction was carried out in solution (3M) for 10 minutes. The nickel ions on the surface of the fabric are finally reduced into nickel nano particles, so that the catalytic activation of the nickel nano particles is realized.
4) Chemical plating of alloys
Immediately after activation of the nickel nanoparticles, the fabric was immersed in 500ml of Ni-W-P alloy electroless plating solution and heated at a constant temperature of 70 ℃ for 60 minutes. The solvent of the Ni-W-P alloy chemical plating solution is deionized water, and the concentrations of various solutes in the solution are respectively as follows: 40g/L of nickel sulfate hexahydrate, 40g/L of sodium tungstate dihydrate, 15g/L of ammonium citrate, 20g/L of sodium hypophosphite and a pH value of 9.5. After removal from the electroless plating solution, the fabric samples were rinsed with deionized water and placed in an 80 ℃ oven to facilitate surface drying. Finally, the carbon fiber fabric coated with the Ni-W-P ternary alloy is obtained.
Scanning the prepared flexible wearable conductive material by an electron microscope, as shown in fig. 12, fig. 12 is a scanning electron microscope image of the novel flexible wearable conductive material prepared in this embodiment.
FIGS. 13 to 15 are graphs of Joule heating behavior of the composite material prepared in example 3 at different applied voltages, and experiments show that the composite material can reach a heating temperature of 35 ℃ within 30s under the condition of 1V applied voltage; under the condition of 1.5V electrifying voltage, the heating temperature of 53 ℃ can be reached within 60 s; under the condition of 2V electrifying voltage, the heating temperature of 107 ℃ can be reached within 30s, and the composite material is proved to have excellent heating efficiency and joule heating temperature range. FIG. 16 is a graph of multiple cycle Joule heating behavior of the composite material prepared in example 3 under a 2V energization voltage, with experimental results showing: after the composite material is subjected to single, 20 and 50 times of cyclic heating, the heating performance and efficiency of the composite material are not greatly changed, and the heating stability of the composite material is proved. The conductivity of the composite material was measured with a conductivity meter (Lei Chen instrument, model DDS-307) to obtain a conductivity of 4.35 × 103S/m shows that the prepared flexible wearable conductive material has good conductive performance.
Comparative example 1:
a preparation method of a flexible wearable conductive material with Joule heating performance comprises the following steps:
1) ultrasonic cleaning of carbon fiber substrate surface
The carbon fiber fabric is cut into a square with the size of 10cm multiplied by 10cm, the square is sequentially placed in ethanol and deionized water to carry out ultrasonic cleaning on the surface, and then rinsing and drying are carried out on the surface.
2) Modifying the surface of a carbon fiber matrix by using a KH550 silane coupling agent solution
The fabric is soaked in a 3% KH550 solution for 30 minutes, the solvent is ethanol, and then the fabric is dried in an oven at 120 ℃.
3) Autocatalytic activation of nickel nanoparticles
Preliminarily preparing a nickel ion solution, wherein the nickel ion solution is prepared by dissolving nickel sulfate hexahydrate and sodium hypophosphite in deionized water, and the preparation method comprises the following steps: the concentrations of the nickel sulfate hexahydrate solution and the sodium hypophosphite solution are respectively 20g/L and 30 g/L. The surface-modified fabric was immersed in a nickel ion solution at room temperature for 10 minutes.
Then, the soaked fabric is placed in NaBH4The reaction was carried out in solution (0.5M) for 10 minutes. The nickel ions on the surface of the fabric are finally reduced into nickel nano particles, so that the catalytic activation of the nickel nano particles is realized.
4) Chemical plating of alloys
Immediately after activation of the nickel nanoparticles, the fabric was immersed in 500ml of Ni — P alloy electroless plating solution and heated at a constant temperature of 90 ℃ for 40 minutes. The solvent of the Ni-P alloy chemical plating solution is deionized water, and the concentrations of various solutes in the solution are respectively as follows: 20g/L of nickel sulfate hexahydrate, 15g/L of ammonium citrate, 15g/L of sodium hypophosphite and a pH value of 10. After removal from the electroless plating solution, the fabric samples were rinsed with deionized water and placed in a 60 ℃ oven to facilitate surface drying. Finally, the carbon fiber fabric coated with the Ni-P ternary alloy is obtained.
The conductivity of the composite material was measured with a conductivity meter (Lei Chen instrument, model DDS-307) to obtain a conductivity of 4.95 × 103And (5) S/m. FIG. 17 is a heat generation performance test chart of the composite material prepared in the example under a 5V electrification voltage condition, and it can be seen that it has almost no heat generation performance.
Comparative example 2:
a preparation method of a flexible wearable conductive material with Joule heating performance comprises the following steps:
1) ultrasonic cleaning of carbon fiber substrate surface
The carbon fiber fabric is cut into a square with the size of 10cm multiplied by 10cm, the square is sequentially placed in ethanol and deionized water to carry out ultrasonic cleaning on the surface, and then rinsing and drying are carried out on the surface.
2) Autocatalytic activation of nickel nanoparticles
Preliminarily preparing a nickel ion solution, wherein the nickel ion solution is prepared by dissolving nickel sulfate hexahydrate and sodium hypophosphite in deionized water, and the preparation method comprises the following steps: the concentrations of the nickel sulfate hexahydrate solution and the sodium hypophosphite solution are respectively 20g/L and 30 g/L. The fabric with the cleaned surface was immersed in a nickel ion solution at room temperature for 10 minutes.
Then, the soaked fabric is placed in NaBH4The reaction was carried out in solution (0.5M) for 10 minutes. The nickel ions on the surface of the fabric are finally reduced into nickel nano particles, so that the catalytic activation of the nickel nano particles is realized.
3) Chemical plating of alloys
Immediately after activation of the nickel nanoparticles, the fabric was immersed in 500ml of Ni-W-P alloy electroless plating solution and heated at a constant temperature of 90 ℃ for 40 minutes. The solvent of the Ni-W-P alloy chemical plating solution is deionized water, and the concentrations of various solutes in the solution are respectively as follows: 20g/L of nickel sulfate hexahydrate, 5g/L of sodium tungstate dihydrate, 15g/L of ammonium citrate, 15g/L of sodium hypophosphite and a pH value of 10. After removal from the electroless plating solution, the fabric samples were rinsed with deionized water and placed in a 60 ℃ oven to facilitate surface drying. The conductivity test was carried out on it and it was found that it was not conductive.
Comparative example 3:
a preparation method of a flexible wearable conductive material with Joule heating performance comprises the following steps:
1) ultrasonic cleaning of carbon fiber substrate surface
The carbon fiber fabric is cut into a square with the size of 10cm multiplied by 10cm, the square is sequentially placed in ethanol and deionized water to carry out ultrasonic cleaning on the surface, and then rinsing and drying are carried out on the surface.
2) Modifying the surface of a carbon fiber matrix by adopting a pure KH550 silane coupling agent
The fabric is soaked in pure KH550 solution for 30 minutes and then dried in an oven at 120 ℃.
3) Autocatalytic activation of nickel nanoparticles
Preliminarily preparing a nickel ion solution, wherein the nickel ion solution is prepared by dissolving nickel sulfate hexahydrate and sodium hypophosphite in deionized water, and the preparation method comprises the following steps: the concentrations of the nickel sulfate hexahydrate solution and the sodium hypophosphite solution are respectively 20g/L and 30 g/L. The surface-modified fabric was immersed in a nickel ion solution at room temperature for 10 minutes.
Then, the soaked fabric is placed in NaBH4The reaction was carried out in solution (0.5M) for 10 minutes. The nickel ions on the surface of the fabric are finally reduced into nickel nano particles, so that the catalytic activation of the nickel nano particles is realized.
4) Chemical plating of alloys
Immediately after activation of the nickel nanoparticles, the fabric was immersed in 500ml of Ni-W-P alloy electroless plating solution and heated at a constant temperature of 90 ℃ for 40 minutes. The solvent of the Ni-W-P alloy chemical plating solution is deionized water, and the concentrations of various solutes in the solution are respectively as follows: 20g/L of nickel sulfate hexahydrate, 5g/L of sodium tungstate dihydrate, 15g/L of ammonium citrate, 15g/L of sodium hypophosphite and a pH value of 10. After removal from the electroless plating solution, the fabric samples were rinsed with deionized water and placed in a 60 ℃ oven to facilitate surface drying. The prepared material was subjected to a conductivity test and found not to have conductivity.
Comparative example 4:
a preparation method of a flexible wearable conductive material with Joule heating performance comprises the following steps:
1) ultrasonic cleaning of carbon fiber substrate surface
The carbon fiber fabric is cut into a square with the size of 10cm multiplied by 10cm, the square is sequentially placed in ethanol and deionized water to carry out ultrasonic cleaning on the surface, and then rinsing and drying are carried out on the surface.
2) Modifying the surface of a carbon fiber matrix by using a KH550 silane coupling agent solution
The fabric is soaked in a 3% KH550 solution for 30 minutes, the solvent is ethanol, and then the fabric is dried in an oven at 120 ℃.
3) Tungsten nanoparticle autocatalytic activation
Preliminarily preparing a tungsten ion solution, wherein the tungsten ion solution is prepared by dissolving sodium tungstate dihydrate and sodium hypophosphite in deionized water, and the preparation method comprises the following steps: the concentrations of the sodium tungstate dihydrate solution and the sodium hypophosphite solution are respectively 20g/L and 30 g/L. The fabric with the modified surface is soaked in a tungsten ion solution for 10 minutes at room temperature.
Then, the soaked fabric is placed in NaBH4The reaction was carried out in solution (0.5M) for 10 minutes. It was found that the tungsten ions on the surface of the fabric were not reduced to tungsten nanoparticles.
The foregoing basic embodiments of the invention and their various further alternatives can be freely combined to form multiple embodiments, all of which are contemplated and claimed herein. In the scheme of the invention, each selection example can be combined with any other basic example and selection example at will. Numerous combinations will be known to those skilled in the art.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents and improvements made within the spirit and principle of the present invention are intended to be included within the scope of the present invention.

Claims (8)

1. A preparation method of a flexible nickel-tungsten-phosphorus ternary alloy coating coated carbon fiber fabric is characterized by comprising the following steps: the method adopts a flexible wearable conductive material with Joule heating performance, the material takes flexible carbon fiber as a substrate, a conductive coating of nickel-tungsten-phosphorus ternary alloy is arranged on the surface of the flexible carbon fiber substrate, and the conductive coating of the nickel-tungsten-phosphorus ternary alloy is prepared in a chemical plating way;
the preparation method comprises the following steps:
s1: placing the carbon fiber fabric in ethanol and deionized water in sequence, ultrasonically cleaning the surface, rinsing and drying the carbon fiber fabric, and removing grease and impurities;
s2: soaking the fabric processed in the step S1 in a KH550 silane coupling agent solution, and then placing the fabric in an oven for drying;
s3: preparing a nickel ion solution, soaking the surface-modified fabric obtained in the step S2 in the nickel ion solution at room temperature, then placing the soaked fabric in a sodium borohydride solution, and finally reducing the nickel ions on the surface of the fabric into nickel nanoparticles to realize the catalytic activation of the nickel nanoparticles;
s4: and immediately immersing the activated carbon fiber fabric into a nickel-tungsten-phosphorus alloy chemical plating solution after activation of the nickel nano particles, taking out the activated carbon fiber fabric from the chemical plating solution, washing a fabric sample with deionized water, and putting the fabric sample into an oven for surface drying to obtain the nickel-tungsten-phosphorus ternary alloy coated carbon fiber fabric.
2. The method for preparing the flexible nickel-tungsten-phosphorus ternary alloy coating-coated carbon fiber fabric as claimed in claim 1, wherein the method comprises the following steps: the KH550 silane coupling agent solution in S2 has a mass concentration of 0.5-10% and ethanol as solvent, and is mixed and sealed in a cool and dry place for 0.5-48 hours for use.
3. The method for preparing the flexible nickel-tungsten-phosphorus ternary alloy coating-coated carbon fiber fabric as claimed in claim 1, wherein the method comprises the following steps: in S3, the nickel nanoparticles are activated by autocatalysis.
4. The method for preparing the flexible nickel-tungsten-phosphorus ternary alloy coating-coated carbon fiber fabric as claimed in claim 1, wherein the method comprises the following steps: the nickel ion solution in S3 is prepared by dissolving nickel sulfate hexahydrate and sodium hypophosphite in deionized water, wherein: the concentrations of the nickel sulfate hexahydrate and the sodium hypophosphite solution are respectively 5-50g/L and 5-30 g/L.
5. The method for preparing the flexible nickel-tungsten-phosphorus ternary alloy coating-coated carbon fiber fabric as claimed in claim 1, wherein the method comprises the following steps: the concentration of the sodium borohydride solution in the S3 is 0.5-8M.
6. The method for preparing the flexible carbon fiber fabric coated with the nickel-tungsten-phosphorus ternary alloy coating according to claim 1, wherein the concentrations of solutes in the nickel-tungsten-phosphorus alloy electroless plating solution in S4 are respectively as follows: 5-50g/L of nickel sulfate hexahydrate, 5-50g/L of sodium tungstate dihydrate, 10-50g/L of ammonium citrate and 5-30g/L of sodium hypophosphite.
7. The method for preparing the flexible nickel-tungsten-phosphorus ternary alloy coating-coated carbon fiber fabric as claimed in claim 1, wherein the method comprises the following steps: the pH value of the chemical plating solution in the S4 is 8-11.5.
8. The method for preparing the flexible nickel-tungsten-phosphorus ternary alloy coating-coated carbon fiber fabric as claimed in claim 1, wherein the method comprises the following steps: the chemical plating temperature in S4 is 50-95 deg.C, and the time is 10-120 min.
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