CN116376058A - Aramid nanofiber conductive hydrogel and preparation method and application thereof - Google Patents
Aramid nanofiber conductive hydrogel and preparation method and application thereof Download PDFInfo
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- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/02—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques
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Abstract
The invention provides an aramid nanofiber conductive hydrogel and a preparation method and application thereof, and belongs to the technical field of conductive hydrogels. The preparation method is simple in preparation process, good in biocompatibility and suitable for large-scale industrial application. In addition, through high-pressure homogenization treatment, the uniform dispersion of the conductive substance in the aramid nanofiber solution is realized, the problem of nonuniform mixing of the conductive filler in the traditional method is avoided, and the method has extremely high use value.
Description
Technical Field
The invention relates to the technical field of conductive hydrogels, in particular to an aramid nanofiber conductive hydrogel, a preparation method and application thereof.
Background
The hydrogel is a high molecular polymer with a three-dimensional network structure, which is obtained by crosslinking hydrophilic polymer chains in water, can keep a certain shape in water but is not dissolved by water, shows excellent water absorption and water retention property and gel stability, and can be used as a good matrix, carrier or skeleton of a functional soft material. The hydrogel is taken as a substrate, and the conductive hydrogel can be obtained by adding a conductive material. Compared with the traditional hydrogel, the conductive hydrogel has the characteristics of both hydrogel materials and conductive materials, has good biocompatibility and unique conductivity, and becomes a potential candidate material in the fields of tissue engineering, flexible wearable electronic equipment, implantation electrodes, biosensors and the like.
Carbon-based nanomaterials, such as Carbon Nanotubes (CNT), graphene Oxide (GO), carbon fibers, and the like, are considered as conductive materials with great development prospects due to their unique properties of high conductivity, environmental stability, good biocompatibility, and the like. By introducing the nano particles with high conductivity into the hydrogel to form a permeable particle network, the conductivity and mechanical properties of the hydrogel can be effectively improved.
In the current research, although there are a large number of conductive hydrogels used for smart mechanical materials, preparing conductive hydrogels with high conductivity and excellent mechanical properties is still a significant technical challenge. The non-uniform distribution of the conductive particles in the hydrogel severely affects its conductivity and mechanical properties. And most of conductive hydrogels need to be introduced with substances such as cross-linking agents, initiators, doping agents and the like in the preparation process, the preparation process is complex, the biocompatibility is poor, and the application of the conductive hydrogels in the fields of biomedicine and the like is limited.
Para-aramid nanofibers (Aramid Nanofibers, ANFs) have unique nanoscale structures, large length-diameter ratios and specific surface areas, and simultaneously retain excellent mechanical properties, good thermal stability and chemical stability of the aramid fibers. Therefore, ANFs and their hydrogels have received great attention in various fields of materials science, engineering, chemistry, and polymer science. The ANFs hydrogel can be obtained through solvent exchange, and the formed hydrogel has good mechanical properties. However, existing manufacturing processes are complex and time consuming. In order to further expand the application range of the ANFs hydrogel, a simple method for preparing the aramid nanofiber conductive hydrogel is urgently needed.
Therefore, the problems of uneven mixing of the conductive filler and complex preparation process of the conventional conductive hydrogel are needed to be solved at present.
Disclosure of Invention
The invention aims to solve the problems of uneven mixing of conductive fillers and complex preparation process of the traditional conductive hydrogel, and provides the aramid nanofiber conductive hydrogel, the preparation method and the application thereof, which are simple in operation, excellent in conductive performance and good in biocompatibility, and have wide application prospects in various fields such as electronic skin, biosensors, supercapacitors, flexible wearable electronic equipment and the like.
The invention is realized by the following technical scheme:
the preparation method of the aramid nanofiber conductive hydrogel comprises the following steps:
step one: para-aramid fiber in DMSO/KOH/H 2 Mixing the O system to obtain an aramid nanofiber solution;
step two: carrying out ultrasonic stirring on the aramid nanofiber solution obtained in the first step and a conductive material, and homogenizing under high pressure to obtain a mixed solution;
step three: pouring the mixed solution obtained in the second step into a mould, and then placing the mould into a closed container containing a protonated solvent for standing to obtain initial hydrogel;
step four: and (3) placing the initial hydrogel obtained in the step (III) into deionized water for solvent exchange to obtain the aramid nanofiber conductive hydrogel.
Further, the concentration of the aramid nanofiber solution in the first step is 0.5-10 mg/mL.
Further, in the second step, the mass ratio of the aramid nanofiber solution to the conductive material is (50-80): (50-20), wherein the conductive material is one or more of carbon nanotubes, graphene, MXene, carbon fibers, metal and oxide nanoparticles thereof.
Further, warm water, methanol, ethanol, formic acid, acetic acid or hydrochloric acid is adopted as the protonated solvent in the step three, the temperature of the protonated solvent is 25-90 ℃, and the standing time is 6-48 h.
Further, in the first step, the mixing mode is full stirring, the stirring rotating speed is 800-1600 rpm, the stirring temperature is 30-70 ℃, and the stirring time is 4-48 h.
Further, in the second step, the stirring speed is 800-1600 rpm, the stirring time is 4-48 h, the ultrasonic power is 700-1500W, the ultrasonic time is 5-20 min, the homogenizing pressure is 800-1600 bar, and the homogenizing times are 10-30 times.
Further, the shape of the die in the third step comprises a round shape, a rectangular shape and a honeycomb shape, and the volume of the die is 10-200 mL.
Further, the solvent exchange time in the fourth step is 6-48 h.
The aramid nanofiber conductive hydrogel is prepared by the preparation method.
The application of the aramid nanofiber conductive hydrogel comprises the steps of pre-freezing the aramid nanofiber conductive hydrogel, and then performing freeze drying treatment to obtain the aramid nanofiber conductive aerogel.
Compared with the prior art, the invention has the following beneficial technical effects:
the invention provides a preparation method of an aramid nanofiber conductive hydrogel, which can simply, quickly and efficiently realize the conductivity of the hydrogel. Through high-pressure homogenization, the uniform dispersion of the conductive substance in the solution is realized, and the problem of nonuniform mixing of the conductive filler in the traditional method is avoided. In addition, in the preparation process of the conductive hydrogel, the aramid nanofibers in the solution are protonated by the steam of the protonated solvent, so that the process is simple, the complex crosslinking process in the traditional method for directly preparing the conductive hydrogel compound is effectively reduced, and the application field of the structure is greatly improved.
The concentration of the aramid nanofiber solution can be controlled, so that the aramid nanofiber conductive hydrogel with different transparency and mechanical properties can be prepared. When the mass fraction of the aramid nanofiber in the aramid nanofiber solution is lower than 0.1%, the prepared aramid nanofiber conductive hydrogel is weak in mechanical strength and good in transparency; when the mass fraction of the aramid nanofiber in the aramid nanofiber solution is higher than 1%, the prepared aramid nanofiber conductive hydrogel has good mechanical properties and poor transparency. The transparency of conductive hydrogels is an important property that is required in the field of flexible sensor visualization. The aramid nanofiber conductive hydrogel with transparency can transmit electric signals under the condition of not blocking optical signals, and the application of the aramid nanofiber conductive hydrogel in the field of intelligent devices is expanded. In addition, when the conductive hydrogel is used as a strain or pressure sensor and is stretched or compressed from outside, the internal network structure of the conductive hydrogel changes, so that the electrical property of the conductive hydrogel changes. When the hydrogel is subjected to external pressure, the hydrogel is compressed to enable the network structure to become compact, and the resistance of the gel is also reduced; when the conductive hydrogel is stretched and deformed, the conductive network is stretched, so that the electrical resistance of the hydrogel increases. Therefore, the aramid nanofiber conductive hydrogel with different mechanical properties can be prepared according to the requirements, can be used for indicating external pressure or stretching changes according to the changes of the resistance or the conductivity, and has potential application value in the field of wearable flexible equipment.
The preparation method does not introduce extra cross-linking agent, initiator, doping agent and other substances in the preparation process of the conductive hydrogel, has simple preparation process and good biocompatibility, and has wide application prospect in various fields such as electronic skin, biosensors, supercapacitors, flexible wearable electronic equipment and the like. The preparation method of the invention can be also suitable for preparing other types of hydrogel, has universality, simple operation and low cost, and is suitable for large-scale industrial application.
According to the invention, the aramid nanofiber conductive hydrogel with different geometric shapes, such as honeycomb shape, firewood pile shape, rice shape, snowflake shape and the like, can be prepared by selecting different molds according to requirements, so that the application range of the aramid nanofiber conductive hydrogel is greatly expanded.
Drawings
FIG. 1 is a flow chart of the preparation process of the invention;
FIG. 2 is a photograph of an aramid nanofiber conductive hydrogel obtained in example 1 of the present invention.
Detailed Description
The invention is further described below:
the preparation method of the aramid nanofiber conductive hydrogel comprises the following steps:
step (1): para-aramid fiber in DMSO/KOH/H 2 Fully stirring in the O system to obtain the aramid nanofiber solution, wherein the stirring speed is 800-1600 rpm, the stirring temperature is 30-70 ℃, the stirring time is 4-48 h, and the concentration of the aramid nanofiber solution is 0.5-10 mg/mL.
Step (2): the aramid nanofiber solution obtained in the step (1) and the conductive material are subjected to ultrasonic stirring according to the mass ratio of (50-80) (50-20), and then high-pressure homogenization to obtain a mixed solution, wherein the stirring speed is 800-1600 rpm, the stirring time is 4-48 h, the ultrasonic power is 700-1500W, the ultrasonic time is 5-20 min, the homogenizing pressure is 800-1600 bar, the homogenizing times are 10-30, and the conductive material is one or more of carbon nano tubes, graphene, MXene, carbon fibers, metals, oxide nano particles and the like.
Step (3): pouring the mixed solution obtained in the step (2) into a mould, and then placing the mould into a closed container containing a protonated solvent for standing to obtain initial hydrogel; the shape of the die comprises a round shape, a rectangular shape and a honeycomb shape, and the volume of the die is 10-200 mL; the protonated solvent adopts warm water, methanol, ethanol, formic acid, acetic acid or hydrochloric acid, the temperature of the protonated solvent is 25-90 ℃, and the standing time is 6-48 h.
Step (4): and (3) placing the initial hydrogel obtained in the step (3) into deionized water for solvent exchange to obtain the aramid nanofiber conductive hydrogel. The solvent exchange time is 6-48 h.
The aramid nanofiber conductive hydrogel is prepared by the preparation method.
The application of the aramid nanofiber conductive hydrogel comprises the steps of pre-freezing the aramid nanofiber conductive hydrogel, and then performing freeze drying treatment to obtain the aramid nanofiber conductive aerogel.
Aiming at the problems of complex and time-consuming preparation process, poor biocompatibility, poor mechanical property and the like of the traditional conductive hydrogel, the invention provides a preparation method of the aramid nanofiber conductive hydrogel. The preparation method disclosed by the invention is simple and efficient in preparation process, good in biocompatibility of the aramid nanofiber conductive hydrogel, and wide in application prospect in various fields such as electronic skin, biosensors, supercapacitors, flexible wearable electronic equipment and the like.
The invention is further illustrated by the following examples:
example 1
Step (1): para-aramid fiber in DMSO/KOH/H 2 Stirring in O system for 4 hr at 800rpm and 30deg.C to obtain a solution dispersed in DMSO/KOH/H 2 An aramid nanofiber solution in an O mixed system; wherein the concentration of the aramid nanofiber solution is 0.5mg/mL;
step (2): adding the carbon nano tube into the aramid nanofiber solution obtained in the step (1) (the mass ratio of the aramid nanofiber to the carbon nano tube is 50:50), stirring, wherein the stirring speed is 800rpm, the stirring time is 4 hours, the ultrasonic power is 700W, the ultrasonic time is 5 minutes, the high-pressure homogenization is 800bar, and the homogenization times are 10 times, so as to obtain a uniformly mixed solution;
step (3): pouring the mixed solution obtained in the step (2) into a circular mold with the volume of 10mL, placing the circular mold into a closed container containing 25 ℃ methanol solution, and standing for 6h to obtain initial hydrogel;
step (4): and (3) placing the initial hydrogel obtained in the step (3) into deionized water, and exchanging the solvent for 6 hours to obtain the aramid nanofiber conductive hydrogel.
Pre-freezing the aramid nanofiber conductive hydrogel obtained in the step (4), and performing freeze drying treatment to obtain the aramid nanofiber conductive aerogel.
Example 2
Step (1): para-aramid fiber in DMSO/KOH/H 2 Stirring in O system for 48 hr at 1600rpm and 70 deg.C to obtain the product dispersed in DMSO/KOH/H 2 An aramid nanofiber solution in an O mixed system; wherein the concentration of the aramid nanofiber solution is 10mg/mL;
step (2): adding graphene into the aramid nanofiber solution obtained in the step (1) (the mass ratio of the aramid nanofibers to the graphene is 80:20), stirring at 1600rpm for 48 hours, performing ultrasonic treatment, wherein the ultrasonic power is 1500W, the ultrasonic time is 20 minutes, homogenizing under high pressure, the homogenizing pressure is 1600bar, and the homogenizing times are 30 times, so as to obtain a uniformly mixed solution;
step (3): pouring the mixed solution obtained in the step (2) into a rectangular die with the volume of 200mL, placing the rectangular die into a closed container filled with warm water at 90 ℃, and standing for 48 hours to obtain initial hydrogel;
step (4): and (3) placing the initial hydrogel obtained in the step (3) into deionized water, and exchanging solvents for 48 hours to obtain the aramid nanofiber conductive hydrogel.
Pre-freezing the aramid nanofiber conductive hydrogel obtained in the step (4), and performing freeze drying treatment to obtain the aramid nanofiber conductive aerogel.
Example 3
Step (1): para-aramid fiber in DMSO/KOH/H 2 Stirring in O system for 24 hr at 1200rpm and 50 deg.C to obtain the final product dispersed in DMSO/KOH/H 2 An aramid nanofiber solution in an O mixed system; wherein the concentration of the aramid nanofiber solution is 5mg/mL;
step (2): adding the carbon nano tube into the aramid nanofiber solution obtained in the step (1) (the mass ratio of the aramid nanofiber to the carbon nano tube is 65:35), stirring, wherein the stirring speed is 1200rpm, the stirring time is 24 hours, the ultrasonic power is 1000W, the ultrasonic time is 10 minutes, the high-pressure homogenization is 1200bar, and the homogenization times are 20 times, so as to obtain a uniformly mixed solution;
step (3): pouring the mixed solution obtained in the step (2) into a honeycomb-shaped mold with the volume of 100mL, placing the honeycomb-shaped mold into a closed container containing ethanol solution with the temperature of 50 ℃, and standing for 24 hours to obtain initial hydrogel;
step (4): and (3) placing the initial hydrogel obtained in the step (3) into deionized water, and exchanging solvents for 24 hours to obtain the aramid nanofiber conductive hydrogel.
Pre-freezing the aramid nanofiber conductive hydrogel obtained in the step (4), and performing freeze drying treatment to obtain the aramid nanofiber conductive aerogel.
Example 4
Step (1): para-aramid fiber in DMSO/KOH/H 2 Stirring in O system for 12 hr at 1500rpm and 30deg.C to obtain a solution dispersed in DMSO/KOH/H 2 An aramid nanofiber solution in an O mixed system; wherein the concentration of the aramid nanofiber solution is 5mg/mL;
step (2): adding the ferroferric oxide powder into the aramid nanofiber solution obtained in the step (1) (the mass ratio of the aramid nanofiber to the ferroferric oxide powder is 60:40), stirring, wherein the stirring speed is 1000rpm, the stirring time is 4 hours, the ultrasonic power is 1000W, the ultrasonic time is 20 minutes, the high-pressure homogenization is carried out, the homogenization pressure is 1000bar, and the homogenization times are 30 times, so as to obtain a uniformly mixed solution;
step (3): pouring the mixed solution obtained in the step (2) into a circular mold with the volume of 50mL, placing the circular mold into a closed container containing 25 ℃ hydrochloric acid solution, and standing for 6h to obtain initial hydrogel;
step (4): and (3) placing the initial hydrogel obtained in the step (3) into deionized water, and exchanging the solvent for 6 hours to obtain the aramid nanofiber conductive hydrogel.
Pre-freezing the aramid nanofiber conductive hydrogel obtained in the step (4), and performing freeze drying treatment to obtain the aramid nanofiber conductive aerogel.
Example 5
Step (1): para-aramid fiber in DMSO/KOH/H 2 Stirring in O system for 4 hr at 1600rpm and 50 deg.C to obtain the product dispersed in DMSO/KOH/H 2 An aramid nanofiber solution in an O mixed system; wherein the concentration of the aramid nanofiber solution is 2mg/mL;
step (2): adding carbon fibers into the aramid nanofiber solution obtained in the step (1) (the mass ratio of the aramid nanofibers to the carbon fibers is 80:20), stirring at a stirring speed of 800rpm for 4 hours, performing ultrasonic treatment at an ultrasonic power of 700W for 5 minutes, homogenizing under high pressure at a homogenizing pressure of 800bar for 10 times to obtain a uniformly mixed solution;
step (3): pouring the mixed solution obtained in the step (2) into a circular mold with the volume of 50mL, placing the circular mold into a closed container containing 30 ℃ formic acid solution, and standing for 6h to obtain initial hydrogel;
step (4): and (3) placing the initial hydrogel obtained in the step (3) into deionized water, and exchanging the solvent for 6 hours to obtain the aramid nanofiber conductive hydrogel.
Pre-freezing the aramid nanofiber conductive hydrogel obtained in the step (4), and performing freeze drying treatment to obtain the aramid nanofiber conductive aerogel.
Example 6
Step (1): para-aramid fiber in DMSO/KOH/H 2 Stirring in O system for 4 hrThe rotational speed is 1600rpm, the temperature is 50 ℃, and the catalyst is dispersed in DMSO/KOH/H 2 An aramid nanofiber solution in an O mixed system; wherein the concentration of the aramid nanofiber solution is 5mg/mL;
step (2): adding MXene into the aramid nanofiber solution obtained in the step (1) (the mass ratio of the aramid nanofiber to the MXene is 70:30), stirring, wherein the stirring speed is 800rpm, the stirring time is 4 hours, the ultrasonic power is 700W, the ultrasonic time is 5 minutes, the high-pressure homogenization is carried out, the homogenization pressure is 800bar, and the homogenization times are 10 times, so as to obtain a uniformly mixed solution;
step (3): pouring the mixed solution obtained in the step (2) into a circular mold with the volume of 50mL, placing the circular mold into a closed container containing ethanol solution with the temperature of 30 ℃, and standing for 6h to obtain initial hydrogel;
step (4): and (3) placing the initial hydrogel obtained in the step (3) into deionized water, and exchanging the solvent for 6 hours to obtain the aramid nanofiber conductive hydrogel.
Pre-freezing the aramid nanofiber conductive hydrogel obtained in the step (4), and performing freeze drying treatment to obtain the aramid nanofiber conductive aerogel.
Example 7
Step (1): para-aramid fiber in DMSO/KOH/H 2 Stirring in O system for 4 hr at 1600rpm and 50 deg.C to obtain the product dispersed in DMSO/KOH/H 2 An aramid nanofiber solution in an O mixed system; wherein the concentration of the aramid nanofiber solution is 5mg/mL;
step (2): adding MXene and graphene into the aramid nanofiber solution obtained in the step (1) (the mass ratio of the aramid nanofiber to the MXene to the graphene is 80:10:10), stirring, wherein the stirring speed is 800rpm, the stirring time is 4 hours, the ultrasonic power is 700W, the ultrasonic time is 5min, the high-pressure homogenization is carried out, the homogenization pressure is 800bar, and the homogenization times are 10 times, so as to obtain a uniformly mixed solution;
step (3): pouring the mixed solution obtained in the step (2) into a circular mold with the volume of 50mL, placing the circular mold into a closed container containing acetic acid solution at the temperature of 30 ℃, and standing for 6 hours to obtain initial hydrogel;
step (4): and (3) placing the initial hydrogel obtained in the step (3) into deionized water, and exchanging the solvent for 6 hours to obtain the aramid nanofiber conductive hydrogel.
Pre-freezing the aramid nanofiber conductive hydrogel obtained in the step (4), and performing freeze drying treatment to obtain the aramid nanofiber conductive aerogel.
Example 8
Step (1): para-aramid fiber in DMSO/KOH/H 2 Stirring in O system for 4 hr at 1600rpm and 30 deg.c to obtain the water dispersed in DMSO/KOH/H 2 An aramid nanofiber solution in an O mixed system; wherein the concentration of the aramid nanofiber solution is 5mg/mL;
step (2): adding the carbon nano tube and the carbon fiber into the aramid nano fiber solution obtained in the step (1) (the mass ratio of the aramid nano fiber to the carbon nano tube to the carbon fiber is 80:10:10), stirring, wherein the stirring speed is 800rpm, the stirring time is 4 hours, the ultrasonic power is 700W, the ultrasonic time is 5 minutes, the high-pressure homogenization is carried out, the homogenization pressure is 800bar, and the homogenization times are 10 times, so as to obtain a uniformly mixed solution;
step (3): pouring the mixed solution obtained in the step (2) into a circular mold with the volume of 50mL, placing the circular mold into a closed container containing 25 ℃ hydrochloric acid solution, and standing for 6h to obtain initial hydrogel;
step (4): and (3) placing the initial hydrogel obtained in the step (3) into deionized water, and exchanging the solvent for 6 hours to obtain the aramid nanofiber conductive hydrogel.
Pre-freezing the aramid nanofiber conductive hydrogel obtained in the step (4), and performing freeze drying treatment to obtain the aramid nanofiber conductive aerogel.
Claims (10)
1. The preparation method of the aramid nanofiber conductive hydrogel is characterized by comprising the following steps of:
step one: para-aramid fiber in DMSO/KOH/H 2 Mixing the O system to obtain an aramid nanofiber solution;
step two: carrying out ultrasonic stirring on the aramid nanofiber solution obtained in the first step and a conductive material, and homogenizing under high pressure to obtain a mixed solution;
step three: pouring the mixed solution obtained in the second step into a mould, and then placing the mould into a closed container containing a protonated solvent for standing to obtain initial hydrogel;
step four: and (3) placing the initial hydrogel obtained in the step (III) into deionized water for solvent exchange to obtain the aramid nanofiber conductive hydrogel.
2. The method for preparing an aramid nanofiber conductive hydrogel according to claim 1, wherein the concentration of the aramid nanofiber solution in the step one is 0.5-10 mg/mL.
3. The preparation method of the aramid nanofiber conductive hydrogel according to claim 1, wherein in the second step, the mass ratio of the aramid nanofiber solution to the conductive material is (50-80): (50-20), and the conductive material is one or more of carbon nanotubes, graphene, MXene, carbon fibers, metal and oxide nanoparticles thereof.
4. The method for preparing the aramid nanofiber conductive hydrogel according to claim 1, wherein in the third step, warm water, methanol, ethanol, formic acid, acetic acid or hydrochloric acid is adopted as the protonating solvent, the temperature of the protonating solvent is 25-90 ℃, and the standing time is 6-48 hours.
5. The method for preparing the aramid nanofiber conductive hydrogel according to claim 1, wherein the mixing mode in the first step is full stirring, the stirring speed is 800-1600 rpm, the stirring temperature is 30-70 ℃, and the stirring time is 4-48 h.
6. The method for preparing the aramid nanofiber conductive hydrogel according to claim 1, wherein the stirring speed in the second step is 800-1600 rpm, the stirring time is 4-48 h, the ultrasonic power is 700-1500W, the ultrasonic time is 5-20 min, the homogenizing pressure is 800-1600 bar, and the homogenizing times are 10-30 times.
7. The method for preparing an aramid nanofiber conductive hydrogel according to claim 1, wherein the shape of the mold in the third step comprises a round shape, a rectangular shape and a honeycomb shape, and the volume of the mold is 10-200 mL.
8. The method for preparing an aramid nanofiber conductive hydrogel according to claim 1, wherein the solvent exchange time in the fourth step is 6-48 hours.
9. An aramid nanofiber conductive hydrogel prepared by the preparation method of any one of claims 1-8.
10. The use of the aramid nanofiber conductive hydrogel of claim 9 in the preparation of an aramid nanofiber conductive aerogel.
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