阅读说明：本技术 一种多功能可穿戴聚合物/MXene复合织物加热器及其制备方法 (Multifunctional wearable polymer/MXene composite fabric heater and preparation method thereof ) 是由 王建峰 刘晓雅 李雷 王万杰 张晓朦 曹艳霞 杨艳宇 于 2020-05-13 设计创作，主要内容包括：本发明涉及柔性可穿戴织物,具体涉及一种多功能可穿戴聚合物/MXene复合织物加热器及其制备方法；聚合物/MXene复合织物加热器的制备方法,包括以下步骤：(1)将聚合物基织物在碱溶液中浸泡后洗涤,制得预处理聚合物基织物；(2)将LiF粉末和HCl溶液搅拌,制得刻蚀液；(3)将MAX相粉末加入刻蚀液中搅拌,制得反应产物；将反应产物稀释后离心,去除上清液,制得沉淀物MXene；向沉淀物MXene中加入去离子水,先超声再离心,制得MXene溶液；(4)将预处理聚合物基织物在MXene溶液中浸渍后,取出后干燥,制得聚合物/MXene复合织物加热器。本发明制得的聚合物/MXene复合织物加热器厚度为340μm时,其电磁屏蔽效能为42.1 dB,同时其还具有良好的透气、阻燃和抗菌功能。(The invention relates to a flexible wearable fabric, in particular to a multifunctional wearable polymer/MXene composite fabric heater and a preparation method thereof, wherein the preparation method of the polymer/MXene composite fabric heater comprises the following steps of (1) soaking a polymer base fabric in an alkaline solution and then washing the polymer base fabric to prepare a pretreated polymer base fabric, (2) stirring L iF powder and an HCl solution to prepare an etching solution, (3) adding MAX phase powder into the etching solution to stir to prepare a reaction product, diluting the reaction product and then centrifuging the reaction product to remove supernatant to prepare a precipitate MXene, adding deionized water into the precipitate MXene, firstly performing ultrasonic treatment and then centrifuging to prepare an MXene solution, and (4) soaking the pretreated polymer base fabric in the MXene solution, taking out and drying the soaked polymer base fabric to prepare the polymer/MXene composite fabric heater.)

1. A preparation method of a multifunctional wearable polymer/MXene composite fabric heater is characterized by comprising the following steps:

(1) pretreating, namely soaking the polymer-based fabric in an alkali solution for 1-4 hours at 50-90 ℃, stirring, and washing the soaked polymer-based fabric with deionized water to obtain a pretreated polymer-based fabric;

(2) preparing etching liquid, and stirring L iF powder and HCl solution at room temperature to react to prepare HF etching liquid;

(3) preparing MXene solution, adding MAX phase powder into the HF etching solution at 20-50 ℃, and stirring at the rotating speed of 100-1000 rpm for reaction to obtain a reaction product; then, diluting the reaction product with deionized water, centrifuging at the rotating speed of 3000-5000 rpm, removing the supernatant, and repeatedly centrifuging until the pH value is more than or equal to 6 to obtain a precipitate MXene; finally, adding deionized water into the MXene precipitate, performing ultrasonic treatment and centrifuging at the rotating speed of 3000-5000 rpm to prepare MXene solution;

(4) preparing a polymer/MXene composite fabric heater, dipping the pretreated polymer-based fabric in MXene solution, taking out, and drying in a vacuum oven at 50-80 ℃ to obtain the polymer/MXene composite fabric heater.

2. The preparation method of the multifunctional wearable polymer/MXene composite fabric heater according to claim 1, wherein in step (1), the polymer-based fabric is one or more of terylene, acrylon, chinlon, vinylon, aramid fiber and cotton fabric; the alkali solution is 5-20 wt% of NaOH solution, and the pH value of the polymer-based fabric washed by deionized water is 6-8.

3. The preparation method of the multifunctional wearable polymer/MXene composite fabric heater according to claim 2, wherein in the step (2), the mass of the L iF powder is 1-100 g, the volume and concentration of HCl are 100-3000 m L and 6-15 mol/L respectively, and the stirring reaction time is 30-60 min.

4. The preparation method of the multifunctional wearable polymer/MXene composite fabric heater according to claim 3, wherein in the step (3), the mass of the MAX phase powder is 1-100 g, and the concentration of the MXene solution is 0.5-20 mg/m L.

5. The preparation method of the multifunctional wearable polymer/MXene composite fabric heater according to any one of claims 1 to 4, wherein in the step (4), the dipping is performed at least once, and the time of each dipping is 1-30 min.

6. The preparation method of the multifunctional wearable polymer/MXene composite fabric heater according to claim 5, wherein in the step (4), the inhibition rate of the polymer/MXene composite fabric heater to Escherichia coli and Bacillus subtilis is as high as 99%; the maximum electromagnetic shielding effectiveness of the polymer/MXene composite fabric heater is more than or equal to 42.1 dB.

7. The method for preparing the multifunctional wearable polymer/MXene composite fabric heater according to claim 5, wherein in the step (4), the applied voltage for the electrothermal transformation of the polymer/MXene composite fabric heater is in a range of 0.1-20V, and the temperature range which can be reached by the electrothermal transformation of the polymer/MXene composite fabric heater is in a range of 5-220 ℃.

8. The preparation method of the multifunctional wearable polymer/MXene composite fabric heater according to claim 5, wherein in the step (4), the light source for the photothermal conversion of the polymer/MXene composite fabric heater is one or more of near infrared light, far infrared light and sunlight; the maximum temperature of the photothermal conversion of the polymer/MXene composite fabric heater was 204 ℃.

9. A multifunctional wearable polymer/MXene composite fabric heater is characterized by being prepared by the preparation method of claims 1-8.

10. Use of the multifunctional wearable polymer/MXene composite fabric heater of claim 9 in the fields of wearable fabric, fabric electric heater, fabric optical heater, heat converter.

Technical Field

The invention relates to a flexible wearable fabric, in particular to a multifunctional wearable polymer/MXene composite fabric heater and a preparation method thereof.

Background

Wearable heaters have received much attention because of their great application value in heat preservation, thermotherapy, deicing, defogging, drug delivery, sensors, and the like. Research on materials such as electrothermal or photothermal conversion films/fibers based on metals, indium tin oxide, carbon nanomaterials, conductive polymer composites, and the like has yielded tremendous results. In recent years, the thermal response rate, the temperature range, the working safety, the durability, the controllability and other performances of the wearable heater are remarkably improved; however, the development of wearable heaters with excellent properties such as flexibility, air permeability, flame retardancy, etc. is still a great challenge. Fabrics, especially lightweight, comfortable and breathable commercial polymer textiles, are considered to be ideal substrates for developing flexible, breathable, wearable heaters that can better fit the human body and meet the diverse scenario application requirements.

With advances in technology, a number of researchers have attempted to incorporate electronic components into fabrics to form smart fabrics. Smart fabrics can be used to generate heat energy to the wearer in addition to measuring physiological signals of the wearer. Most intelligent fabrics are composed of chips, yarns, wires and resistors, wherein the wires are embedded or woven in the fabric woven by the yarns and connected to the resistors and the chips; the wire can be connected to an external power source, so that the external power source supplies power to the resistor and the chip.

In addition, the rapid development of wearable electronic devices aggravates electromagnetic radiation pollution and poses great threats to human health. Therefore, there is a demand for wearable heaters based on polymer fabrics to shield electromagnetic radiation. In addition, the long-term high-temperature use of the wearable heater based on the fabric brings great thermal failure risk, and even brings disasters such as fire disasters to human health. Furthermore, the temperature rise creates bacteria that cause cross-contamination and is another hazard to the use of wearable heaters. Therefore, the wearable polymer-based fabric heater with the functions of electromagnetic shielding, fire prevention, antibiosis and the like has great significance and is the development direction of the next generation wearable heater.

MXene, a novel two-dimensional crystal material, belongs to graphene-like materials and is considered to be a better substitute for graphene and other carbon nano materials. MXene of two-dimensional material can be prepared by etching MAX phase by wet chemical method, and general formula is M_n+1X_nT_XWherein M is a transition metal, X is carbon or nitrogen, T represents a terminal group, O, F, H and the like. MXene has adjustable surface groups, excellent conductivity and super-large specific surface area, is used as a conductive material for capacitors or batteries, and can also be used for energy storage or electromagnetic shielding; meanwhile, MXene has nearly one hundred percent of photo-thermal conversion performance; in addition, MXene also has excellent flame retardant property and antibacterial effect. However, the polymer-based fabric heater using MXene as filler lacks research on wearability, flame retardance, antibacterial property and electromagnetic shielding effect.

Disclosure of Invention

Technical problem to be solved

Aiming at the defects of the prior art, the invention provides the multifunctional wearable polymer/MXene composite fabric heater and the preparation method thereof, so that the polymer/MXene composite fabric heater has stable and rapid electric-heat and photo-thermal conversion performances, and excellent electromagnetic shielding, antibacterial, air permeability and flame retardant performances.

(II) technical scheme

In order to achieve the purpose, the invention is realized by the following technical scheme:

a preparation method of a multifunctional wearable polymer/MXene composite fabric heater comprises the following steps:

(1) pretreating, namely soaking the polymer-based fabric in an alkali solution for 1-4 hours at 50-90 ℃, stirring, and washing the soaked polymer-based fabric with deionized water to obtain a pretreated polymer-based fabric;

(2) preparing etching liquid, and stirring L iF powder and HCl solution at room temperature to react to prepare HF etching liquid;

(3) preparing MXene solution, adding MAX phase powder into the HF etching solution at 20-50 ℃, and stirring at the rotating speed of 100-1000 rpm for reaction to obtain a reaction product; then, diluting the reaction product with deionized water, centrifuging at the rotating speed of 3000-5000 rpm, removing the supernatant, and repeatedly centrifuging until the pH value is more than or equal to 6 to obtain a precipitate MXene; finally, adding deionized water into the MXene precipitate, performing ultrasonic treatment and centrifuging at the rotating speed of 3000-5000 rpm to prepare MXene solution;

(4) preparing a polymer/MXene composite fabric heater, dipping the pretreated polymer-based fabric in MXene solution, taking out, and drying in a vacuum oven at 50-80 ℃ to obtain the polymer/MXene composite fabric heater.

Preferably, in the step (1), the polymer-based fabric is one or more of terylene, acrylon, chinlon, vinylon, aramid fiber and cotton fabric; the aqueous alkali is 5-20 wt% of NaOH solution, and the pH value of the polymer-based fabric washed by deionized water is 6-8.

Preferably, in the step (2), the mass of the L iF powder is 1-100 g, the volume and the concentration of HCl are 100-3000 m L and 6-15 mol/L respectively, and the stirring reaction time is 30-60 min.

Preferably, in the step (3), the mass of the MAX phase powder is 1-100 g, and the concentration of the MXene solution is 0.5-20 mg/m L.

Preferably, in the step (4), the impregnation is carried out at least once, and the time of each impregnation is 1-30 min.

Preferably, in the step (4), the inhibition rate of the polymer/MXene composite fabric heater to escherichia coli and bacillus subtilis is as high as 99%; the maximum electromagnetic shielding effectiveness of the polymer/MXene composite fabric heater is equal to or more than 42.1 dB.

Preferably, in the step (4), the range of the applied voltage for the electrothermal conversion of the polymer/MXene composite fabric heater is 0.1-20V, and the temperature range which can be reached by the electrothermal conversion of the polymer/MXene composite fabric heater is 5-220 ℃.

Preferably, in the step (4), the light source for photothermal conversion of the polymer/MXene composite fabric heater is one or more of near infrared light, far infrared light and sunlight; the maximum temperature of the photothermal conversion of the polymer/MXene composite fabric heater was 204 ℃.

A multifunctional wearable polymer/MXene composite fabric heater is prepared by the preparation method.

The multifunctional wearable polymer/MXene composite fabric heater can be applied to the fields of wearable fabrics, fabric electric heaters, fabric optical heaters and heat converters.

(III) advantageous effects

When the thickness of the polymer/MXene composite fabric heater prepared by the invention is 340 mu m, the electromagnetic shielding efficiency is 42.1 dB, and the polymer/MXene composite fabric heater also has good flame retardant and antibacterial functions; the polymer/MXene composite fabric heater prepared by the method has good air permeability and durability, and meets wearable requirements; the preparation method provided by the invention is simple and safe, and can be used for large-scale batch production.

Drawings

FIG. 1 is a scanning electron microscope image of a heater made of PET/MXene composite fabric according to example 3 of the present invention;

FIG. 2 is a graph showing the experimental air permeability of the PET/MXene composite fabric heater according to example 3 of the present invention;

FIG. 3 is a graph showing electromagnetic shielding effectiveness of the PET/MXene composite fabric heater according to embodiments 1 to 3 of the present invention;

FIG. 4 is a combustion state diagram of a PET/MXene composite fabric heater manufactured in examples 1 to 3 of the present invention;

FIG. 5 is an experimental chart of the antibacterial performance of the PET/MXene composite fabric heater prepared in the embodiments 1-3 of the present invention;

FIG. 6 is a graph of electrothermal conversion performance of the PET/MXene composite fabric heater prepared in example 3 of the present invention under different applied voltages;

FIG. 7 is a graph showing the photothermal conversion performance of the PET/MXene composite fabric heater according to example 3 of the present invention under different laser irradiation distances;

FIG. 8 is a graph showing the photothermal conversion performance of the PA/MXene composite fabric heater according to example 4 of the present invention under irradiation of far infrared light from different distances;

FIG. 9 is a graph showing the photothermal conversion performance of the PA/MXene composite fabric heater prepared in example 4 of the present invention under sunlight irradiation.

Detailed Description

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 will be clearly and completely described below with reference to the embodiments of the present invention, and it is obvious that the described embodiments are some embodiments of the present invention, but not all embodiments. 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.

A preparation method of a multifunctional wearable polymer/MXene composite fabric heater comprises the following steps:

(1) pretreating, namely soaking the polymer-based fabric in a 5-20 wt% NaOH solution at 50-90 ℃, stirring and reacting for 1-4 h, and then washing the soaked polymer-based fabric with ionized water until the pH value is 6-8 to obtain a pretreated polymer-based fabric;

(2) preparing an etching solution, stirring and reacting 1-100 g of L iF powder and 100-3000 m of L of 6-15 mol/L HCl solution in a polytetrafluoroethylene cup for 30-60 min at room temperature to prepare an in-situ HF etching solution;

(3) preparing MXene solution, adding 1-100 g of MAX phase powder into HF etching solution, carrying out magnetic stirring reaction for 20-30 h under the conditions that the temperature is 20-50 ℃ and the rotating speed is 100-1000 rpm to obtain a reaction product, diluting the prepared reaction product with deionized water, pouring the diluted reaction product into a centrifugal tube, centrifuging for 5-10 min at the rotating speed of 3000-5000 rpm to remove centrifugal supernatant, repeatedly centrifuging until the pH value is not less than 6 to obtain precipitate MXene, adding deionized water into the precipitate MXene, carrying out ultrasonic treatment for 5-20 min, and centrifuging for 5-10 min at the rotating speed of 3000-5000 rpm to obtain the MXene solution with the concentration of 0.5-20 mg/m L;

(4) preparing a polymer/MXene composite fabric heater, dipping the pretreated polymer base fabric in MXene solution for 1-30 min, and then transferring to a vacuum oven for drying at 50-80 ℃ to obtain the polymer/MXene composite fabric heater.

Wherein the polymer base fabric is one or more of terylene, acrylon, chinlon, vinylon, aramid fiber and cotton fabric; MAX phase powder is Ti₃AlC₂、Ti₂At least one of AlC.