CN112663323B - MXene electromagnetic shielding fabric and preparation method and application thereof - Google Patents
MXene electromagnetic shielding fabric and preparation method and application thereof Download PDFInfo
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- CN112663323B CN112663323B CN202011408077.4A CN202011408077A CN112663323B CN 112663323 B CN112663323 B CN 112663323B CN 202011408077 A CN202011408077 A CN 202011408077A CN 112663323 B CN112663323 B CN 112663323B
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Abstract
The invention relates to an MXene electromagnetic shielding fabric and a preparation method and application thereof. The method comprises the following steps: pretreating a flexible fabric substrate by plasma, then soaking the flexible fabric substrate in MXene dispersion liquid, taking out the flexible fabric substrate, drying the flexible fabric substrate, and adding CO 2 And (4) annealing treatment at low temperature under the condition. The electromagnetic shielding fabric has good flexibility, water washing resistance and electromagnetic shielding property.
Description
Technical Field
The invention belongs to the field of electromagnetic shielding materials and preparation and application thereof, and particularly relates to an MXene electromagnetic shielding fabric and a preparation method and application thereof.
Background
With the rapid development of modern electronic technologies, electronic devices and wireless communication devices are widely used, and then more and more electromagnetic radiation and interference are generated, so that the space electromagnetic environment is increasingly complex. Electromagnetic radiation becomes a new type of pollution following noise, water and air pollution, not only affecting the information security of communication equipment and the normal operation of electronic equipment, but also endangering human health. Therefore, research into new electromagnetic shielding materials has become an indispensable part for protecting electronic components and human beings from electromagnetic interference.
The metal and metal oxide materials which are applied to the electromagnetic shielding field firstly have the defects of large density, poor chemical corrosion resistance, difficult processing and the like, so that the requirements of people on the light weight and high efficiency of the electromagnetic shielding material are difficult to meet. Low-dimensional nano materials such as carbon nano tube, graphene, MXene and the like gradually become the preparation of electromagnetic interference due to the characteristics of small density, high conductivity, easiness in processing and the likeThe desired choice of shielding material. Wherein, the novel two-dimensional nano material MXene has high conductivity (8000S/cm) and high electron mobility (5.03 multiplied by 103 cm) due to a special structure and abundant surface functional groups 2 V · s), good biocompatibility, and diversified morphology, have great research prospects in functional materials. Meanwhile, MXene belongs to a normal-temperature photo-thermal conversion far-infrared high-radiation material, has high photo-thermal conversion rate, does not need a heat source, and has the characteristic of absorbing environmental heat and outputting the environmental heat in a far-infrared energy form. The single-layer MXene film can realize 20% of effective shielding of electromagnetic waves, the 24-layer (about 55nm in thickness) film has 99% of electromagnetic shielding performance (20 dB), and the absolute shielding performance value reaches 3.89 x 106dB cm 2 The value is obviously superior to most of the electromagnetic shielding materials reported in the literature at present. However, most of the MXene-based flexible electromagnetic shielding composite materials are mainly prepared by filling MXene in a polymer material. Such as patent: a preparation method of an electrostatic spinning polyimide/MXene electromagnetic shielding film (publication number: CN 111155239A), an aqueous polyurethane-MXene electromagnetic shielding bionic nano composite material film and a preparation method (publication number: CN 11069847A) and the like are characterized in that a polymer stock solution obtained after monomer polymerization is mixed with MXene dispersion liquid, and the composite material is prepared through simple suction filtration. Can not be well applied to wearable and other directions needing electromagnetic shielding, and the coating of the high polymer material greatly reduces the conductivity of the composite material. The research of MXene-based high-performance electromagnetic shielding fabric is not complete.
Disclosure of Invention
The technical problem to be solved by the invention is to provide an MXene electromagnetic shielding fabric and a preparation method and application thereof, so as to overcome the defects of poor electromagnetic shielding effect and poor durability of the electromagnetic shielding fabric in the prior art.
The invention provides an MXene electromagnetic shielding fabric, which is prepared by uniformly dip-coating a pretreated flexible fabric substrate in MXene dispersion liquid, drying, and then adding the mixture into CO 2 Calcining under the condition, wherein the annealing treatment process parameters are as follows: placing the dried fabric in a rapid heating furnace in CO 2 Heating to 60 deg.C at a rate of 10-20 deg.C/s for 20-40min in atmosphere, and preheatingThen heating to 60-80 ℃ at the same speed, treating for 24-36h, closing the rapid heating furnace, and preserving heat for 2-4h.
The flexible fabric substrate is one of non-woven fabric, pure cotton cloth, ketone ammonia fiber cloth, pure linen cloth and bamboo fiber cloth.
The MXene dispersion is prepared by mixing MAX phase Ti 3 AlC 2 Adding into etching solution of lithium fluoride, hydrochloric acid and ultrapure water, stirring for reaction, centrifuging, dispersing the obtained precipitate in deionized water, centrifuging again, and collecting the dispersion solution.
The Ti 3 AlC 2 And the mass ratio of LiF to HCl to ultrapure water is 1-2.
The stirring reaction temperature is 25-30 ℃, and the stirring reaction time is 22-26 h.
The invention also provides a preparation method of the MXene electromagnetic shielding fabric, which comprises the following steps:
(1) Plasma pre-treating a flexible fabric substrate;
(2) Dipping the flexible fabric substrate pretreated in the step (1) in MXene dispersion liquid, taking out and drying;
(3) And (3) annealing the dried fabric to obtain the MXene electromagnetic shielding fabric, wherein the annealing process parameters are as follows:
placing the dried fabric in a rapid heating furnace in CO 2 Heating to 60 ℃ at the speed of 10-20 ℃/s for preheating for 20-40min under the atmosphere, then heating to 60-80 ℃ at the same speed, treating for 24-36h, closing the rapid heating furnace, and then preserving heat for 2-4h.
The plasma pretreatment in the step (1) comprises the following steps: using a plasma processor in an atmosphere of O 2 The power is 50-70W, and the processing time is 3-8min.
The flexible fabric substrate in the step (1) comprises but is not limited to one of non-woven fabric, pure cotton cloth, ketoamine fiber cloth, pure linen cloth and bamboo fiber cloth.
The preparation method of the MXene dispersion liquid in the step (2) comprises the following steps: subjecting the MAX phase Ti 3 AlC 2 Adding into etching solution of lithium fluoride, hydrochloric acid and ultrapure water, stirring for reaction,centrifuging, dispersing the obtained precipitate in deionized water, centrifuging again, and collecting the dispersion, wherein Ti is 3 AlC 2 And the mass ratio of LiF to HCl to ultrapure water is 1-2.
The concentration of the MXene dispersion liquid in the step (2) is 5-10mg/mL.
The stirring reaction temperature is 25-30 ℃, the stirring reaction time is 22-26 h, and the stirring speed is 650-750 r/min.
The centrifugation is repeated multiple times until the pH of the supernatant is close to 7.
The speed of the multiple centrifugation is 3000-4000 r/min, and the centrifugation time is 3-8min each time.
The speed of the secondary centrifugation is 3000-4000 r/min, and the time of the secondary centrifugation is 3-8min.
The invention also provides application of the MXene electromagnetic shielding fabric in wearable clothes.
The fabric has higher strength, the MXene has good adhesion capacity on the surface of the fabric and high stability, the MXene and the fabric have the advantages of no toxicity, good biocompatibility and the like, the fabric has excellent skin-friendly property, is breathable and comfortable when contacting with a human body, and meets the requirements of the wearable field.
The fabric substrate is put into MXene dispersion liquid for impregnation, and after drying, the fabric substrate is put into CO 2 And annealing at low temperature under the condition to obtain the MXene electromagnetic shielding fabric with the P-N junction microstructure on the surface. This is due to Ti 3 C 2 T x -MXene in CO 2 Evolution of the surface structure after atmospheric heat treatment. Ti prepared by chemical etching method 3 C 2 T x -MXene having a large number of-OH, -O and-F groups on the surface to ensure Ti 3 C 2 T x The structure is stable. In the heat treatment process, the exposed Ti layer on the outermost surface layer and the surface oxygen-containing group are subjected to oxidation reaction to generate anatase TiO 2 While with increasing temperature anatase is partly converted to the more thermally stable rutile phase TiO 2 . The oxidation reaction of the Ti atomic layer exposes the middle C layer, and forms an amorphous carbon phase of a two-dimensional lamellar layer. The reaction process enables the MXene conductive layer on the surface of the fabric to be the most conductive layerForming TiO on the outer layer at local position 2 The P-N junction microstructure of the-C is beneficial to improving the wave absorbing performance of the MXene electromagnetic shielding fabric.
The calcination treatment of MXene is not a very novel treatment method, but the calcination at high temperature is usually used in the prior art, and Ar is used as a protective gas. Professor Yury Gogotsi, the father of MXene, published an article of International society of Electromagnetic Waves by 2D Transition Metal carbide Ti in the Science of the International Top-level journal 3 CNT x (MXene).[Aamir Iqbal,et al.Anomalous Absorption of Electromagnetic Waves by 2D Transition Metal Carbonitride Ti 3 CNT x (MXene),Science,2020.DOI:10.1126]. In this work the investigators used temperatures of 150 c, 250 c, and 350 c, respectively, to subject MXene to a thermal calcination treatment in an Ar atmosphere, although higher calcination temperatures resulted in decreased interlamellar spacing, but increased pore size and pore volume due to increased oxidation of the material. After calcination, the electromagnetic wave generated by the layered metamaterial-like structure is extremely high in absorption, and the electromagnetic shielding effect is respectively improved to 77dB,99dB and 116dB. An article named Weizai Baio, et al, facil Synthesis of crushed Nitrogen-Doped MXene Nanosheets as A New Sulfur Host for Lithium-Sulfur Batteries, published by professor Wang Dan, proceedings of the Process engineering of Chinese academy in the adv.Energy Mater.journal (J.].Advanced Energy Materials,2018,8(13).]. Using negatively charged Ti 3 C 2 T x After the sheet and the positively charged melamine are annealed, the wrinkled N-Ti is successfully prepared by electrostatic self-assembly 3 C 2 T x Nanosheet material, with N atoms successfully doped into Ti 3 C 2 T x A material. The annealing method still uses high-temperature short-time calcination, but the annealing method and the reason for improving the electromagnetic shielding performance are different from other works. The annealing method used by the invention is low-temperature long-time annealing, so that the MXene nanosheets loaded on the outermost layer of the MXene conducting layer on the surface of the fabric are fully and uniformly calcined, and CO is used 2 As a calcining gas, toMXene nano-sheets on the outermost layer are completely oxidized to form TiO at partial positions of the outermost layer 2 -P-N junction microstructure of C. The surface of the composite fabric forms more heterogeneous interfaces, increases the electron concentration at the interfaces, and increases the transmission path of electromagnetic waves inside the material. And form a miniature capacitor-like circuit, these structural characteristics will enhance Ti 3 C 2 T x The electromagnetic wave absorbing ability of (1). In addition, ti is not destroyed in the interior after the heat treatment process 3 C 2 T x On the premise of the two-dimensional structure, a large number of surface functional groups are reduced, and an amorphous carbon phase is stripped, so that the conductivity of the material is improved, and the increase of the conductivity loss of electromagnetic waves in the material is facilitated. The formation of the low dielectric loss phase titanium dioxide is beneficial to optimizing the impedance matching between the surface of the material and the free space.
Advantageous effects
(1) The MXene electromagnetic shielding fabric has good flexibility and electromagnetic shielding characteristics, and has biocompatibility and environmental friendliness.
(2) The invention utilizes the characteristics of loose fabric fiber and rough surface structure, adopts MXene to modify the flexible fabric material, constructs and designs the MXene electromagnetic shielding fabric with the three-dimensional network structure, effectively improves the wave absorbing performance of the traditional electromagnetic shielding fabric, is applied to wearable clothing, and has great significance for protecting human health and reducing the harm of electromagnetic radiation.
(3) The method uses low-temperature long-time annealing to uniformly calcine the MXene nanosheets loaded on the outermost layer of the MXene conductive layer on the surface of the fabric, and uses CO 2 The MXene nano-sheets at the outermost layer are completely oxidized by using the sacrificial gas as the calcining gas, and TiO is formed at the partial position of the outermost layer 2 -P-N junction microstructure of C. The wave absorbing performance of the MXene electromagnetic shielding fabric is improved, and the washing durability of the fabric is improved.
(4) The method is simple and easy to implement, low in requirements on production equipment and low in cost.
Drawings
Fig. 1 is a flow chart of the preparation of the MXene electromagnetic shielding fabric of the present invention.
Fig. 2 is an XRD pattern of MXene prepared in example 1.
Fig. 3 shows FESEM images of the MXene film prepared in example 1 before and after low temperature annealing treatment, wherein (a) shows the MXene film without low temperature annealing treatment, and (b) shows the MXene film with P-N junction microstructure after low temperature annealing treatment.
Fig. 4 shows FESEM images of the purified cotton fabric (a-c) prepared in example 1 and the MXene electromagnetic shielding purified cotton fabric (d-f) obtained in step (4) of example 1 at different magnifications.
Fig. 5 is electromagnetic shielding effectiveness of the MXene electromagnetic shielding pure cotton fabric subjected to low temperature annealing treatment prepared in example 1, the original pure cotton fabric and the MXene electromagnetic shielding pure cotton fabric not subjected to low temperature annealing treatment prepared in comparative example 1 at X band, wherein (a) the electromagnetic shielding effectiveness is absorbed; (b) reflective electromagnetic shielding effectiveness; (c) total electromagnetic shielding effectiveness; (d) electromagnetic interference shielding efficiency.
Fig. 6 shows MXene electromagnetic shielding cotton garment (c) and its applications (a, b) prepared in example 1, wherein a is unshielded and b is shielded.
Fig. 7 is a V-I curve before and after 30min water washing of the MXene electromagnetic shielding pure cotton fabric (a) not subjected to the low temperature annealing treatment in comparative example 1 and the MXene electromagnetic shielding pure cotton fabric (b) subjected to the low temperature annealing treatment in example 1.
Detailed Description
The invention will be further illustrated with reference to the following specific examples. It should be understood that these examples are for illustrative purposes only and are not intended to limit the scope of the present invention. Further, it should be understood that various changes or modifications of the present invention may be made by those skilled in the art after reading the teaching of the present invention, and such equivalents may fall within the scope of the present invention as defined in the appended claims.
The main reagent sources related to the embodiment of the invention are shown in table 1:
TABLE 1
| Reagent | Chemical formula (II) | Specification of | Manufacturer of the product |
| Lithium fluoride | LiF | Analytical purity | Chinese medicine |
| MAX phase | Ti 3 AlC 2 | Analytical purity | Chinese medicine |
| 36% concentrated hydrochloric acid | HCl | Analytical purity | Chinese medicine |
| Oxygen gas | O 2 | (High purity) | Shenzhong gas |
| Carbon dioxide gas | CO 2 | (High purity) | Shenzhong gas |
Example 1
(1) Preparation process of MXene:
an etching solution of 1.6g LiF, 19.25g HCl and 5.5mL ultrapure water was sufficiently stirred, and 1g MAX phase (Ti) was slowly added 3 AlC 2 ) And (3) stirring the powder at the reaction temperature of 27 ℃ and the stirring speed of 700r/min for 24 hours till complete etching. The washing was performed by multiple centrifugations at 3500r/min until the supernatant pH was close to 7. And then fully dispersing the obtained precipitate in deionized water, centrifuging at 3500r/min for 5min, and collecting the upper black liquid, namely MXene dispersion liquid. Fig. 2 is the XRD pattern of MXene prepared in this example 1, which shows complete MXene etching.
(2) Pretreatment of the fabric:
mixing 2.5X 2.5cm 2 Placing pure cotton cloth (thickness 2 mm) in a plasma processor, setting the power at 60W, processing time at 5min, and processing at O 2 Pretreating the pure cotton cloth under the atmosphere.
(3) And (3) putting the pure cotton cloth pretreated in the step (2) into a culture dish containing the MXene/water dispersion liquid with the concentration of 5mg/mL obtained in the step (1), soaking for 10 minutes, taking out after the soaking is sufficient, and drying by cold air. And repeating the steps of dipping, and regulating and controlling the loading capacity of MXene on the surface of the pure cotton fabric for 3 times.
(4) Low-temperature annealing treatment:
placing the dried MXene/pure cotton composite fabric in a rapid heating furnace in CO 2 Heating to 60 ℃ at the speed of 10 ℃/s in the atmosphere, preheating for 20min, keeping the calcination temperature at 60 ℃ for 24h, closing the rapid heating furnace, keeping the temperature for 2h, and cooling along with the furnace to obtain the MXene electromagnetic shielding pure cotton fabric with the P-N junction microstructure on the surface. Fig. 1 is a flow chart of the preparation of the MXene electromagnetic shielding fabric in example 1. For the effect of the low-temperature annealing treatment on the MXene structure, the MXene obtained in the step (1) is subjected to suction filtration to form a film, and the same low-temperature annealing treatment operation is adopted on the MXene film, as shown in FIG. 3, FIG. 3 is an FESEM image of the MXene film prepared in the example 1 before and after the low-temperature annealing treatment, (a) is the MXene film without the low-temperature annealing treatment, and (b) is the MXene film with the P-N junction microstructure after the low-temperature annealing treatment. It is clearly observed that upon low temperature annealing the layer structure of MXene changes with an increase in monolayer thickness accompanied by a loose microporous structure. Is favorable to electricityThe increase of the electric conduction loss of the magnetic wave in the material proves the effect of the low-temperature annealing treatment on improving the wave absorption performance of the MXene electromagnetic shielding fabric. Fig. 4 shows FESEM images of the pure cotton fabric prepared in example 1 and the MXene electromagnetic shielding pure cotton fabric obtained in step (4) at different magnifications. (a-c) a pure cotton fabric; (d-f) MXene electromagnetic shielding pure cotton fabric. It can be seen that MXene is uniformly coated on the surface of the pure cotton fabric. Fig. 7 is a V-I curve of MXene electromagnetic shielding pure cotton fabrics subjected to low-temperature annealing treatment prepared in example 1 (a) and comparative example 1 (b) before and after 30min water washing. After the MXene electromagnetic shielding fabric subjected to low-temperature annealing treatment is washed by water for 30min, the resistance is increased from 396 omega to 419 omega, and the resistance is only increased by 5%. After the MXene electromagnetic shielding fabric which is not subjected to low-temperature annealing treatment is washed for 30min, the resistance is increased from 408 omega to 890 omega, and the resistance is increased by 118%, so that the washing durability of the fabric is improved simultaneously through the low-temperature annealing treatment.
(5) And (4) carrying out electromagnetic shielding effectiveness test on the MXene electromagnetic shielding pure cotton fabric obtained in the step (4) by using a vector network analyzer. The test frequency is 8.2-12.4GHz, and the frequency step is 0.08GHz. Meanwhile, in order to adapt to the size of the rectangular waveguide, MXene/fabric is made into the size of 22.9 multiplied by 10.2 multiplied by (2.0-6.0) mm, wherein 22.9 multiplied by 10.2mm is the size of the cross section of the rectangular waveguide, and the thickness of a sample is the thickness of the fabric. The result is shown in fig. 5, (fig. 5 is the electromagnetic shielding effectiveness of the MXene electromagnetic shielding pure cotton fabric subjected to low-temperature annealing treatment prepared in example 1, the original pure cotton fabric and the MXene electromagnetic shielding pure cotton fabric not subjected to low-temperature annealing treatment prepared in comparative example 1 in the X waveband, wherein (a) the electromagnetic shielding effectiveness is absorbed, (b) the electromagnetic shielding effectiveness is reflected, (c) the total electromagnetic shielding effectiveness is absorbed, (d) the electromagnetic interference shielding efficiency is obtained, and when the frequency is 10GHz, the total electromagnetic shielding effectiveness, the absorption shielding effectiveness and the reflection shielding effectiveness of the pure cotton fabric are respectively 3.38dB, 2.22dB and 1.17dB, and the total shielding effectiveness is 39.96%; the MXene electromagnetic shielding pure cotton fabric subjected to low-temperature annealing treatment has the total electromagnetic shielding efficiency, the absorption shielding efficiency and the reflection shielding efficiency of 15.77dB, 8.31dB and 7.45dB respectively, and the total shielding efficiency is 85.25 percent. The addition of MXene greatly improves the electromagnetic wave absorption capacity and the reflection capacity of the fabric, and the total shielding effectiveness of the MXene electromagnetic shielding pure cotton fabric in an X wave band is 84.5 percent and is enhanced by more than 1 time than that of the pure cotton fabric (41.6 percent) without the MXene coating.
(6) Combining the area of the ordinary clothes needing shielding with the MXene electromagnetic shielding fabric obtained through the low-temperature annealing treatment in the step (4), and making the MXene electromagnetic shielding pure cotton fabric into a pocket at the position of the heart opening, wherein as shown in FIG. 6, when the MXene electromagnetic shielding pure cotton fabric is not shielded, the radiation detector displays that the electric field radiation intensity is 309.76V/m when the mobile phone dials; the mobile phone is placed in an MXene electromagnetic shielding fabric pocket, and the radiation detector displays that the radiation intensity of an electric field is 0V/m when the mobile phone is dialed. The preparation method of the MXene electromagnetic shielding fabric provided by the invention is applied to wearable clothes, and has great significance in protecting human health and reducing harm of electromagnetic radiation.
Example 2
(1) Preparation process of MXene:
an etching solution of 1g LiF, 12.5g HCl and 5.5mL ultrapure water was sufficiently stirred, and 1g MAX phase (Ti) was slowly added 3 AlC 2 ) And (3) stirring the powder at the reaction temperature of 25 ℃ and the stirring speed of 650r/min for 22 hours till the etching is complete. The washing was carried out by multiple centrifugation at 3000r/min until the supernatant pH was close to 7. And then, fully dispersing the obtained precipitate in deionized water, centrifuging for 3min at 3000r/min, and collecting an upper layer black liquid, namely the MXene dispersion liquid.
(2) Pretreatment of the fabric:
mixing 2.5X 2.5cm 2 The pure linen (thickness 3 mm) is put into a plasma processor, the power is set to be 50W, the processing time is 3min, and the process is carried out at O 2 And (3) pretreating the pure linen in the atmosphere.
(3) And (3) putting the pure linen pretreated in the step (2) into a culture dish containing the MXene/water dispersion liquid with the concentration of 7.5mg/mL obtained in the step (1), soaking for 15 minutes, taking out after full soaking, drying by cold air, repeating the step of soaking, and regulating and controlling the loading amount of the MXene on the surface of the pure linen fabric for 4 times.
(4) Low-temperature annealing treatment:
placing the dried MXene/pure cotton composite fabric in a rapid heating furnace in CO 2 Raising the temperature to the temperature of 15 ℃/s under the atmospherePreheating for 30min at 60 ℃, heating to 70 ℃ at the same heating rate, calcining for 30h, closing the rapid heating furnace, keeping the temperature for 3h, and cooling along with the furnace to obtain the MXene electromagnetic shielding pure linen fabric with the P-N structure on the surface. Fig. 1 is a flow chart of the preparation of the MXene electromagnetic shielding fabric in example 1.
(5) And (5) carrying out electromagnetic shielding effectiveness test on the MXene electromagnetic shielding pure linen fabric obtained in the step (4) by using a vector network analyzer. The test frequency is 8.2-12.4GHz, and the frequency step is 0.08GHz. Meanwhile, in order to adapt to the size of the rectangular waveguide, MXene/fabric is made into the size of 22.9 multiplied by 10.2 multiplied by (2.0-6.0) mm, wherein 22.9 multiplied by 10.2mm is the size of the cross section of the rectangular waveguide, and the thickness of a sample is the thickness of the fabric. When the frequency is 10GHz, the total electromagnetic shielding efficiency, the absorption shielding efficiency and the reflection shielding efficiency of the pure linen fabric are 1.52dB, 1.15dB and 0.37dB respectively; the total electromagnetic shielding effectiveness, the absorption shielding effectiveness and the reflection shielding effectiveness of the MXene electromagnetic shielding fabric are 10.66dB, 6.05dB and 4.61dB respectively, and the total shielding effectiveness is 61.8%. The addition of MXene greatly improves the electromagnetic wave absorption capacity and the reflection capacity of the fabric, and the total shielding effectiveness of the MXene electromagnetic shielding pure hemp fabric in an X wave band is 64 percent and is enhanced by nearly 1 time compared with that of the pure hemp fabric (33.6 percent) without the MXene coating.
(6) Combining the area of the common garment needing shielding with the MXene electromagnetic shielding fabric obtained after the low-temperature annealing treatment in the step (4), and making the MXene electromagnetic shielding pure hemp fabric into a pocket at the position of the heart opening. When the mobile phone is not shielded, the radiation detector displays that the radiation intensity of an electric field is 312.65V/m when the mobile phone dials; the mobile phone is placed in an MXene electromagnetic shielding fabric pocket, and the radiation detector displays that the radiation intensity of an electric field is 13V/m when the mobile phone is dialed. The preparation method of the MXene electromagnetic shielding fabric provided by the invention is applied to wearable clothes, and has great significance in protecting human health and reducing harm of electromagnetic radiation.
Example 3
(1) Preparation process of MXene:
an etching solution of 2g LiF, 30g HCl and 5.5mL of ultrapure water was sufficiently stirred, and 1g of MAX phase (Ti) was slowly added 3 AlC 2 ) Powder, reaction temperature is 30 ℃, stirringThe stirring speed is 750r/min, and the stirring is continued for 26h until the etching is complete. The washing was carried out by multiple centrifugations at 4000r/min until the pH of the supernatant was close to 7. And then fully dispersing the obtained precipitate in deionized water, centrifuging for 8min at 4000r/min, and collecting the upper layer black liquid, namely MXene dispersion liquid.
(2) Pretreatment of the fabric:
2.5X 2.5cm 2 The bamboo fiber cloth (thickness 4 mm) was placed in a plasma processor, the power was set to 70W, the processing time was set to 8min, O 2 Pretreating the bamboo fiber cloth under the atmosphere.
(3) And (3) putting the bamboo fiber cloth pretreated in the step (2) into a culture dish containing the MXene/water dispersion liquid with the concentration of 10mg/mL obtained in the step (1), soaking for 20 minutes, taking out after full soaking, drying by cold air, repeating the step of soaking, and regulating and controlling the loading amount of MXene on the surface of the bamboo fiber fabric for 5 times.
(4) Low-temperature annealing treatment:
placing the dried MXene/bamboo fiber composite fabric in a rapid heating furnace in CO 2 Heating to 60 ℃ at the rate of 20 ℃/s for preheating for 40min under the atmosphere, heating to 80 ℃ at the same heating rate, calcining for 36h, closing the rapid heating furnace, keeping the temperature for 4h, and cooling along with the furnace to obtain the MXene electromagnetic shielding bamboo fiber fabric with the P-N junction microstructure on the surface. Fig. 1 is a flow chart of the preparation of the MXene electromagnetic shielding fabric in example 1.
(5) And (4) carrying out electromagnetic shielding effectiveness test on the MXene electromagnetic shielding bamboo fiber fabric obtained in the step (4) by using a vector network analyzer. The test frequency is 8.2-12.4GHz, and the frequency step is 0.08GHz. Meanwhile, in order to adapt to the size of the rectangular waveguide, MXene/fabric is made into the size of 22.9 multiplied by 10.2 multiplied by (2.0-6.0) mm, wherein 22.9 multiplied by 10.2mm is the size of the cross section of the rectangular waveguide, and the thickness of a sample is the thickness of the fabric. When the frequency is 10GHz, the total electromagnetic shielding effectiveness, the absorption shielding effectiveness and the reflection shielding effectiveness of the bamboo fiber fabric are 1.98dB, 1.65dB and 0.33dB respectively; the total electromagnetic shielding effectiveness, the absorption shielding effectiveness and the reflection shielding effectiveness of the MXene electromagnetic shielding fabric are 12.2dB, 6.87dB and 5.33dB respectively, and the total shielding effectiveness is 75.2%. The addition of MXene greatly improves the electromagnetic wave absorption capacity and reflection capacity of the fabric, and the total shielding effectiveness of the MXene electromagnetic shielding bamboo fiber fabric in an X wave band is 75.2%, which is nearly 1 time enhanced compared with that of the bamboo fiber fabric (38.1%) without the MXene coating.
(6) Combining the area of the common garment needing shielding with the MXene electromagnetic shielding fabric obtained after the low-temperature annealing treatment in the step (4), and making the MXene electromagnetic shielding bamboo fiber fabric into a pocket at the position of the heart opening. When the mobile phone is not shielded, the radiation detector displays that the electric field radiation intensity is 310.36V/m when the mobile phone dials; the mobile phone is placed in an MXene electromagnetic shielding fabric pocket, and the radiation detector displays that the radiation intensity of an electric field is 15V/m when the mobile phone is dialed. The preparation method of the MXene electromagnetic shielding fabric provided by the invention is applied to wearable clothes, and has great significance in protecting human health and reducing harm of electromagnetic radiation.
Comparative example 1
(1) Preparation process of MXene:
mixing 1.6g:19.25g:5.5mL of LiF, HCl and ultrapure water etching solution were fully stirred, and 1g of MAX phase (Ti) was slowly added 3 AlC 2 ) And (3) stirring the powder at the reaction temperature of 27 ℃ and the stirring speed of 700r/min for 24 hours till the etching is complete. Washing was performed by multiple centrifugations at 3500r/min until the supernatant pH was close to 7. And then fully dispersing the obtained precipitate in deionized water, centrifuging at 3500r/min for 5min, and collecting the upper black liquid, namely MXene dispersion liquid. Fig. 2 is the XRD pattern of MXene prepared in this example 1, which shows complete MXene etching.
(2) Pretreatment of the fabric:
mixing 2.5X 2.5cm 2 Placing pure cotton cloth (thickness 2 mm) in a plasma processor, setting the power at 60W, processing time at 5min, and processing at O 2 Pretreating the pure cotton cloth under the atmosphere.
(3) And (3) putting the pure cotton cloth pretreated in the step (2) into a culture dish containing the MXene/water dispersion liquid with the concentration of 5mg/mL obtained in the step (1), soaking for 10 minutes, taking out after the soaking is sufficient, and drying by cold air. And repeating the step of dipping, and regulating and controlling the loading capacity of MXene on the surface of the pure cotton fabric for 3 times to obtain the MXene electromagnetic shielding pure cotton fabric. Fig. 7 is a V-I curve before and after 30min water washing of the MXene electromagnetic shielding pure cotton fabric (a) without low temperature annealing treatment in comparative example 1 and the MXene electromagnetic shielding pure cotton fabric (b) with low temperature annealing treatment in example 1. After the MXene electromagnetic shielding fabric subjected to low-temperature annealing treatment is washed for 30min, the resistance is increased from 396 omega to 419 omega, and the resistance is only increased by 5%. After the MXene electromagnetic shielding fabric which is not subjected to low-temperature annealing treatment is washed for 30min, the resistance is increased from 408 omega to 890 omega, and the resistance is increased by 118%.
(4) And (4) carrying out electromagnetic shielding effectiveness test on the MXene electromagnetic shielding pure cotton fabric obtained in the step (3) by using a vector network analyzer. The test frequency is 8.2-12.4GHz, and the frequency step is 0.08GHz. Meanwhile, in order to adapt to the size of the rectangular waveguide, MXene/fabric is made into the size of 22.9 multiplied by 10.2 multiplied by (2.0-6.0) mm, wherein 22.9 multiplied by 10.2mm is the size of the cross section of the rectangular waveguide, and the thickness of a sample is the thickness of the fabric. As shown in fig. 5, the total electromagnetic shielding effectiveness, the absorption shielding effectiveness and the reflection shielding effectiveness of the MXene electromagnetic shielding fabric subjected to the low-temperature annealing treatment are 15.77dB, 8.31dB and 7.45dB, respectively, and the total shielding effectiveness is 85.25% at a frequency of 10 GHz; the MXene electromagnetic shielding fabric without low-temperature annealing treatment has the total electromagnetic shielding effectiveness, the absorption shielding effectiveness and the reflection shielding effectiveness of 14.28dB, 7.75dB and 6.54dB respectively, and the total shielding effectiveness is 83.2 percent. The electromagnetic wave absorption capacity and reflection capacity of the loaded MXene/pure cotton composite fabric are improved by the low-temperature annealing treatment, and the total shielding efficiency of the MXene electromagnetic shielding pure cotton fabric in an X waveband is enhanced.
(5) Combining an area needing shielding of the ordinary clothes with the MXene electromagnetic shielding fabric obtained in the step (3) without low-temperature annealing treatment, making the MXene electromagnetic shielding pure cotton fabric into a pocket at the position of a heart opening, and when the MXene electromagnetic shielding pure cotton fabric is not shielded, displaying that the radiation intensity of an electric field is 286.23V/m when the mobile phone dials by using a radiation detector; the mobile phone is placed in an MXene electromagnetic shielding fabric pocket, and the radiation detector displays that the radiation intensity of an electric field is 1.2V/m when the mobile phone is dialed.
Claims (8)
1. An MXene electromagnetic shielding fabric is characterized in that a flexible fabric substrate subjected to plasma pretreatment is placed in MXene dispersion liquidDip coating, drying, and then coating with CO 2 Annealing under the condition, wherein the technological parameters of the annealing are as follows: placing the dried fabric in a rapid heating furnace in CO 2 Under the atmosphere, heating to 60 ℃ at the speed of 10-20 ℃/s for preheating for 20-40min, then heating to 60-80 ℃ at the same speed, wherein the treatment time is 24-36h, closing the rapid heating furnace, and then preserving heat for 2-4 h; the MXene dispersion is prepared by mixing MAX phase Ti 3 AlC 2 Adding into etching solution of lithium fluoride, hydrochloric acid and ultrapure water, stirring for reaction, centrifuging, dispersing the obtained precipitate in deionized water, centrifuging again, and collecting the dispersion solution.
2. The MXene electromagnetic shielding fabric of claim 1, wherein the flexible fabric substrate is one of a non-woven fabric, a pure cotton fabric, a ketoamine fiber fabric, a pure linen fabric, and a bamboo fiber fabric.
3. The MXene electromagnetic shielding fabric of claim 1, wherein the Ti is 3 AlC 2 The mass ratio of LiF to HCl to ultrapure water is 1 to 2.
4. The MXene electromagnetic shielding fabric according to claim 1, wherein the stirring reaction temperature is 25 to 30 ℃, and the stirring reaction time is 22 to 26 hours.
5. A preparation method of MXene electromagnetic shielding fabric comprises the following steps:
(1) Plasma pre-treating a flexible fabric substrate;
(2) Dipping the flexible fabric substrate pretreated in the step (1) in MXene dispersion liquid, taking out and drying; the preparation method of the MXene dispersion liquid comprises the following steps: adding a MAX phase Ti 3 AlC 2 Adding into etching solution of lithium fluoride, hydrochloric acid and ultrapure water, stirring for reaction, centrifuging, dispersing the obtained precipitate in deionized water, centrifuging again, and collecting the dispersion solution to obtain Ti 3 AlC 2 The mass ratio of LiF to HCl to ultrapure water is 1 to 12.5 to 30; what is needed isThe stirring reaction temperature is 25 to 30 ℃, and the stirring reaction time is 22 to 26 hours;
(3) And (3) annealing the dried fabric to obtain the MXene electromagnetic shielding fabric, wherein the annealing process parameters are as follows: placing the dried fabric in a rapid heating furnace in CO 2 Heating to 60 ℃ at the speed of 10-20 ℃/s for preheating for 20-40min under the atmosphere, then heating to 60-80 ℃ at the same speed, treating for 24-36h, closing the rapid heating furnace, and then preserving heat for 2-4h.
6. The method of claim 5, wherein the plasma pretreatment in step (1) is: using a plasma processor in an atmosphere of O 2 The power is 50-70W, and the processing time is 3-8min.
7. The method according to claim 5, wherein the concentration of MXene dispersion in step (2) is 5-10mg/mL.
8. Use of the fabric of claim 1 in a wearable garment.
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| CN115787283A (en) * | 2021-09-10 | 2023-03-14 | 北京服装学院 | Preparation method and application of infrared stealth fabric |
| CN113913952B (en) * | 2021-09-29 | 2023-04-14 | 北京航空航天大学 | Polyimide-based electromagnetic shielding film with sandwich structure and preparation method thereof |
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