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
- Publication number
- CN116376058A CN116376058A CN202310342359.6A CN202310342359A CN116376058A CN 116376058 A CN116376058 A CN 116376058A CN 202310342359 A CN202310342359 A CN 202310342359A CN 116376058 A CN116376058 A CN 116376058A
- Authority
- CN
- China
- Prior art keywords
- aramid nanofiber
- aramid
- conductive
- conductive hydrogel
- hydrogel
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 229920003235 aromatic polyamide Polymers 0.000 title claims abstract description 129
- 239000004760 aramid Substances 0.000 title claims abstract description 118
- 239000002121 nanofiber Substances 0.000 title claims abstract description 118
- 239000000017 hydrogel Substances 0.000 title claims abstract description 112
- 238000002360 preparation method Methods 0.000 title claims abstract description 30
- 238000000034 method Methods 0.000 claims abstract description 13
- 238000002156 mixing Methods 0.000 claims abstract description 8
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 57
- 238000003756 stirring Methods 0.000 claims description 50
- 239000000243 solution Substances 0.000 claims description 49
- 239000002904 solvent Substances 0.000 claims description 25
- 239000011259 mixed solution Substances 0.000 claims description 22
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 20
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 13
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 12
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 12
- 239000004964 aerogel Substances 0.000 claims description 11
- 239000002041 carbon nanotube Substances 0.000 claims description 11
- 229910021393 carbon nanotube Inorganic materials 0.000 claims description 11
- 239000004020 conductor Substances 0.000 claims description 11
- 239000008367 deionised water Substances 0.000 claims description 11
- 229910021641 deionized water Inorganic materials 0.000 claims description 11
- 239000000835 fiber Substances 0.000 claims description 11
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 10
- 229920000049 Carbon (fiber) Polymers 0.000 claims description 8
- 239000004917 carbon fiber Substances 0.000 claims description 8
- 229910021389 graphene Inorganic materials 0.000 claims description 8
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 8
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims description 4
- 235000019253 formic acid Nutrition 0.000 claims description 4
- 239000002105 nanoparticle Substances 0.000 claims description 4
- -1 MXene Substances 0.000 claims description 3
- 239000002184 metal Substances 0.000 claims description 3
- 229910052751 metal Inorganic materials 0.000 claims description 3
- 238000000265 homogenisation Methods 0.000 abstract description 19
- 239000000126 substance Substances 0.000 abstract description 5
- 239000011231 conductive filler Substances 0.000 abstract description 4
- 239000006185 dispersion Substances 0.000 abstract description 2
- 238000004108 freeze drying Methods 0.000 description 10
- 238000007710 freezing Methods 0.000 description 10
- 239000000463 material Substances 0.000 description 4
- 239000000047 product Substances 0.000 description 3
- 238000004132 cross linking Methods 0.000 description 2
- 239000003431 cross linking reagent Substances 0.000 description 2
- 239000002019 doping agent Substances 0.000 description 2
- SZVJSHCCFOBDDC-UHFFFAOYSA-N ferrosoferric oxide Chemical compound O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 description 2
- 230000008014 freezing Effects 0.000 description 2
- 239000000499 gel Substances 0.000 description 2
- 239000003999 initiator Substances 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 239000002086 nanomaterial Substances 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 238000009210 therapy by ultrasound Methods 0.000 description 2
- 241000533950 Leucojum Species 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 229920006231 aramid fiber Polymers 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 229920001477 hydrophilic polymer Polymers 0.000 description 1
- 238000002513 implantation Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000009828 non-uniform distribution Methods 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 239000007779 soft material Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 238000012800 visualization Methods 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- 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
- C08J3/03—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques in aqueous media
- C08J3/075—Macromolecular gels
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/28—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof by elimination of a liquid phase from a macromolecular composition or article, e.g. drying of coagulum
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2205/00—Foams characterised by their properties
- C08J2205/02—Foams characterised by their properties the finished foam itself being a gel or a gel being temporarily formed when processing the foamable composition
- C08J2205/026—Aerogel, i.e. a supercritically dried gel
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2377/00—Characterised by the use of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Derivatives of such polymers
- C08J2377/10—Polyamides derived from aromatically bound amino and carboxyl groups of amino carboxylic acids or of polyamines and polycarboxylic acids
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2265—Oxides; Hydroxides of metals of iron
- C08K2003/2275—Ferroso-ferric oxide (Fe3O4)
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/02—Elements
- C08K3/04—Carbon
- C08K3/041—Carbon nanotubes
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/02—Elements
- C08K3/04—Carbon
- C08K3/042—Graphene or derivatives, e.g. graphene oxides
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/10—Metal compounds
- C08K3/14—Carbides
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K7/00—Use of ingredients characterised by shape
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K7/00—Use of ingredients characterised by shape
- C08K7/02—Fibres or whiskers
- C08K7/04—Fibres or whiskers inorganic
- C08K7/06—Elements
Landscapes
- Chemical & Material Sciences (AREA)
- Dispersion Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Processes Of Treating Macromolecular Substances (AREA)
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.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202310342359.6A CN116376058A (en) | 2023-03-31 | 2023-03-31 | Aramid nanofiber conductive hydrogel and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202310342359.6A CN116376058A (en) | 2023-03-31 | 2023-03-31 | Aramid nanofiber conductive hydrogel and preparation method and application thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN116376058A true CN116376058A (en) | 2023-07-04 |
Family
ID=86964052
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202310342359.6A Pending CN116376058A (en) | 2023-03-31 | 2023-03-31 | Aramid nanofiber conductive hydrogel and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN116376058A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN117362743A (en) * | 2023-12-08 | 2024-01-09 | 烟台泰和新材高分子新材料研究院有限公司 | Preparation method of heat-shock-resistant aramid aerogel and aramid aerogel |
Citations (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB698049A (en) * | 1949-08-25 | 1953-10-07 | Bayer Ag | New intermediate products for the production of phthalocyanines |
| FR3039539A1 (en) * | 2015-07-30 | 2017-02-03 | Enersens | MONOLITHIC AEROGEL REINFORCED WITH DISPERSE FIBERS |
| CN108699259A (en) * | 2015-12-30 | 2018-10-23 | 密执安州立大学董事会 | Gel containing ANF and nanocomposite |
| CN110982114A (en) * | 2019-12-11 | 2020-04-10 | 中国科学院苏州纳米技术与纳米仿生研究所 | Aramid fiber/carbon nanotube hybrid aerogel film, and preparation method and application thereof |
| CN111040237A (en) * | 2019-12-25 | 2020-04-21 | 陕西科技大学 | Conductive aramid nanofiber composite aerogel and preparation method thereof |
| CN111040238A (en) * | 2019-12-25 | 2020-04-21 | 陕西科技大学 | Aramid nanofiber/MXene composite conductive aerogel and preparation method thereof |
| CN111235699A (en) * | 2020-01-12 | 2020-06-05 | 哈尔滨工业大学 | Preparation method of nitrogen-modified porous carbon nanofiber aerogel based on aramid nano aerogel |
| CN112250890A (en) * | 2020-10-12 | 2021-01-22 | 哈尔滨工业大学 | Method for preparing chitosan/aramid nanofiber composite hydrogel by standing method |
| CN112980044A (en) * | 2021-03-18 | 2021-06-18 | 航天特种材料及工艺技术研究所 | High-performance bulk aramid nanofiber aerogel and preparation method and application thereof |
| CN115010980A (en) * | 2022-03-09 | 2022-09-06 | 天津工业大学 | Preparation method of aramid aerogel with asymmetric structure |
| CN115160636A (en) * | 2022-08-16 | 2022-10-11 | 南京信息工程大学 | Aramid nano-fiber aerogel balls and preparation method thereof |
| CN115572407A (en) * | 2022-09-09 | 2023-01-06 | 天津科技大学 | Aramid nanofiber-based composite aerogel and preparation method and application thereof |
-
2023
- 2023-03-31 CN CN202310342359.6A patent/CN116376058A/en active Pending
Patent Citations (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB698049A (en) * | 1949-08-25 | 1953-10-07 | Bayer Ag | New intermediate products for the production of phthalocyanines |
| FR3039539A1 (en) * | 2015-07-30 | 2017-02-03 | Enersens | MONOLITHIC AEROGEL REINFORCED WITH DISPERSE FIBERS |
| CN108699259A (en) * | 2015-12-30 | 2018-10-23 | 密执安州立大学董事会 | Gel containing ANF and nanocomposite |
| CN110982114A (en) * | 2019-12-11 | 2020-04-10 | 中国科学院苏州纳米技术与纳米仿生研究所 | Aramid fiber/carbon nanotube hybrid aerogel film, and preparation method and application thereof |
| CN111040237A (en) * | 2019-12-25 | 2020-04-21 | 陕西科技大学 | Conductive aramid nanofiber composite aerogel and preparation method thereof |
| CN111040238A (en) * | 2019-12-25 | 2020-04-21 | 陕西科技大学 | Aramid nanofiber/MXene composite conductive aerogel and preparation method thereof |
| CN111235699A (en) * | 2020-01-12 | 2020-06-05 | 哈尔滨工业大学 | Preparation method of nitrogen-modified porous carbon nanofiber aerogel based on aramid nano aerogel |
| CN112250890A (en) * | 2020-10-12 | 2021-01-22 | 哈尔滨工业大学 | Method for preparing chitosan/aramid nanofiber composite hydrogel by standing method |
| CN112980044A (en) * | 2021-03-18 | 2021-06-18 | 航天特种材料及工艺技术研究所 | High-performance bulk aramid nanofiber aerogel and preparation method and application thereof |
| CN115010980A (en) * | 2022-03-09 | 2022-09-06 | 天津工业大学 | Preparation method of aramid aerogel with asymmetric structure |
| CN115160636A (en) * | 2022-08-16 | 2022-10-11 | 南京信息工程大学 | Aramid nano-fiber aerogel balls and preparation method thereof |
| CN115572407A (en) * | 2022-09-09 | 2023-01-06 | 天津科技大学 | Aramid nanofiber-based composite aerogel and preparation method and application thereof |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN117362743A (en) * | 2023-12-08 | 2024-01-09 | 烟台泰和新材高分子新材料研究院有限公司 | Preparation method of heat-shock-resistant aramid aerogel and aramid aerogel |
| CN117362743B (en) * | 2023-12-08 | 2024-03-08 | 烟台泰和新材高分子新材料研究院有限公司 | Preparation method of heat-shock-resistant aramid aerogel and aramid aerogel |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN109705370B (en) | Preparation method and application method of TEMPO nano-cellulose-polyacrylic acid gel | |
| CN106422995A (en) | Graphene aerogel and hybrid composite material thereof as well as preparation method and application of graphene aerogel | |
| Hu et al. | Tough and stretchable Fe3O4/MoS2/PAni composite hydrogels with conductive and magnetic properties | |
| CN101429336B (en) | Process for producing carbon nano-tube/polyaniline conductive composite material | |
| CN112430352B (en) | Double-network cross-linked and coated polyaniline/multi-walled carbon nanotube composite conductive filler and preparation method thereof | |
| CN107017091A (en) | Nitrogenous multistage porous carbon/graphene composite material and its preparation method and application | |
| CN116376058A (en) | Aramid nanofiber conductive hydrogel and preparation method and application thereof | |
| CN110808175A (en) | Electroactive biomass/polypyrrole hydrogel and preparation method and application thereof | |
| CN107604482B (en) | A kind of N doping porous filamentous nanocarbon and preparation method thereof | |
| Yang et al. | Synthesis of sea urchin-like polystyrene/polyaniline microspheres by seeded swelling polymerization and their catalytic application | |
| CN103146231A (en) | Method for preparing core-shell type carbon nano-tube filling by coating carbon nano-tube through polyionic liquid | |
| CN109847661A (en) | A kind of preparation method of graphene oxide and silver nanowires assembling three-dimensional elasticity hydrogel | |
| CN106046369A (en) | Preparation of polyaniline-graphene layer-layer composite material assisted by supercritical method | |
| Li et al. | Soft conducting polymer hydrogels in situ doped by sulfonated graphene quantum dots for enhanced electrochemical activity | |
| Fu et al. | Novel non-covalent sulfonated multiwalled carbon nanotubes from p-toluenesulfonic acid/glucose doped polypyrrole for electrochemical capacitors | |
| CN110128784A (en) | A kind of preparation method of aqueous carbon hybrid material | |
| CN105174249A (en) | High-performance graphene film and fiber as well as preparation method for high-performance graphene film and fiber by gel transformation | |
| CN112662099A (en) | Stress sensing conductive aerogel and preparation method thereof | |
| Zou et al. | Mechanically strong multifunctional three-dimensional crosslinked aramid nanofiber/reduced holey graphene oxide and aramid nanofiber/reduced holey graphene oxide/polyaniline hydrogels and derived films | |
| CN112210088A (en) | Conductive hydrogel and preparation method and application thereof | |
| CN108484808B (en) | Self-repairing conductive hydrogel based on multiple hydrogen bonds and preparation method thereof | |
| CN1974667A (en) | Prepn process of multiple wall carbon nanotube/polyaniline composite material | |
| Li et al. | Facilely prepared conductive hydrogels based on polypyrrole nanotubes | |
| Dong et al. | Whole-polymers electrode membrane based on the interfacial polymerization and intermacromolecular force between polyaniline and polyethersulfone for flexible supercapacitors | |
| WO2022174502A1 (en) | Anisotropic cellulose-based hydrogel preparation method |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination |