CN113233466A - 3D super-elastic electrospun carbon nanofiber/MXene composite aerogel and synergistic assembly preparation method thereof - Google Patents

3D super-elastic electrospun carbon nanofiber/MXene composite aerogel and synergistic assembly preparation method thereof Download PDF

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CN113233466A
CN113233466A CN202011507412.6A CN202011507412A CN113233466A CN 113233466 A CN113233466 A CN 113233466A CN 202011507412 A CN202011507412 A CN 202011507412A CN 113233466 A CN113233466 A CN 113233466A
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mxene
composite aerogel
carbon nanofiber
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CN113233466B (en
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杨冬芝
秦丽媛
于中振
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Beijing University of Chemical Technology
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Abstract

A3D ultra-elastic electrospun carbon nanofiber/MXene composite aerogel and a synergistic assembly preparation method thereof relate to a nanofiber composite aerogel material. The method is characterized in that one-dimensional carbon nanofibers and two-dimensional MXene with rich surface active sites are used as raw materials, a liquid nitrogen assisted directional freeze-drying technology is adopted, and the 3D nanofiber composite aerogel with a stable anisotropic microchannel structure is assembled by exerting the synergistic effect of one-dimensional and two-dimensional materials, so that the problem of fiber is solved on the one handThe problem of interface contact resistance between the aerogel and the sensor material enables the aerogel to have proper conductivity, and on the other hand, the aerogel is endowed with good elasticity. Shows good sensing response performance and has high sensitivity (65 kPa)‑1) Ultra low detection limit (<5Pa), fast millisecond response (26ms), large operable strain range (0-95%) and excellent response stability.

Description

3D super-elastic electrospun carbon nanofiber/MXene composite aerogel and synergistic assembly preparation method thereof
The technical field is as follows:
the invention belongs to the field of flexible wearable sensor materials, and relates to a nanofiber composite aerogel material.
Background art:
with the popularization of intelligent terminals, wearable electronic equipment presents huge market prospects. The sensor, as one of the core components, will affect the functional design and future development of the wearable device. The flexible wearable electronic sensor has the characteristics of lightness, thinness, portability, excellent electrical performance, high integration level and the like, so that the flexible wearable electronic sensor becomes one of the most concerned electrical sensors. Wearable piezoresistive sensors, as a typical representative of advanced electronic devices, have attracted much attention due to their advantages of high sensitivity, fast frequency response, good stability, and simple and convenient manufacturing.
The aerogel has the characteristics of hierarchical pore structure, good structural stability and electrical conductivity, simple and easy assembling process, quick response to external pressure and the like, and becomes a preferred application material of the wearable piezoresistive sensor. In the past few years, various carbonaceous aerogels, such as carbon nanotube aerogel, carbon nanofiber-based aerogel, graphene-based aerogel and the like, as piezoresistive sensor materials have been widely studied, and 3D electrospun nanofiber aerogel becomes a unique member of the aerogel family with the advantages of high specific surface area, light weight, strong structural design and the like, so that the research on the field of energy storage and conversion is increasingly extensive.
The main deficiency that present 3D nanofiber aerogel is used for wearable pressure drag type sensor is: firstly, the preparation is relatively complex; secondly, the mechanical strength and the rebound resilience are poor; the sensitivity is low, and the main reason is that strong interaction is lacked between fibers in the 3D structure, and irreversible plastic deformation is easy to occur when external load is borne. In view of this, this patent provides a novel, simple method, adopts one-dimensional and two-dimensional material cooperative assembly strategy, solves the fibre aerogel mechanics resilience problem. Specifically, a liquid nitrogen assisted directional freeze-drying technology is utilized to prepare the super-elastic and ultra-light carbon nanofiber/MXene (CNF/MX) composite aerogel with anisotropic micro-channels, CNFs with high length-diameter ratios are mutually entangled and assembled into mutually connected frameworks, and the MXene sheet material enhances the structural stability of the CNF frameworks and enables the aerogel to have proper conductivity. Thanks to the stable directional microchannel structure, the CNF/MX aerogel has an ultra-low density of 4.87mg cm-3It shows excellent compression resilience and structural stability after 5000 cycles of long-term compression at 50% strain, and can withstand 500 cycles at 95% extremely high strain. Importantly, the excellent strain or pressure response characteristics provide the CNF/MX aerogel sensors with high sensitivity (65 kPa)-1) Ultra low detection limit (<5Pa), fast millisecond response (26ms), large operable strain range (0-95%) and excellent response stability. The patent provides a new idea for the preparation of the super elastic fiber aerogel piezoresistive sensor material, and has good application prospect in the field of energy storage and conversion.
The invention content is as follows:
the invention aims to provide a preparation method of a 3D ultra-elastic ultra-light electrospun nanofiber/MXene composite aerogel with anisotropic micro-channels for a wearable sensor material. The method is simple, and the prepared sensor has good sensing response performance.
The technical scheme of the invention is as follows:
A3D ultra-elastic electrospun carbon nanofiber/MXene composite aerogel and a synergistic assembly preparation method thereof are characterized in that: by utilizing the liquid nitrogen-assisted directional freeze drying technology, the carbon nanofiber/MXene composite aerogel has an adjustable anisotropic microchannel structure, CNFs with high length-diameter ratios are mutually entangled and assembled into mutually connected frameworks, and rich oxygen-containing functional groups on the surfaces of MXene nanosheets are tightly combined with the CNFs through the interaction of hydrogen bonds and the like to enhance the structural stability of the CNF frameworks, so that the aerogel has proper conductivity. The stable directional microchannel structure endows the aerogel with excellent mechanical resilience stability and sensing response characteristics.
The 3D super-elastic electrospun carbon nanofiber/MXene composite aerogel and the synergistic assembly preparation method thereof are characterized in that the preparation process comprises the following steps:
(1) preparation of PAN-based carbon nanofibers
First, PVP (preferably M) is addedw58000, adding 3-9 times of PAN (preferably M)w150000), magnetically stirring to obtain uniform spinning solution, and electrostatic spinningThe filament conditions are respectively that the receiving distance is 15-25 cm, the voltage is 12-20 KV, and the electrospinning flow rate is 1-5 mL h-1The received PAN fibrous membrane was vacuum dried at 60 ℃ using grounded aluminum foil as the fiber receiver. Then cutting the PAN nanofiber membrane into sheets, pre-oxidizing the PAN nanofiber membrane for 0.5 to 2 hours at the temperature of 200-250 ℃ in the air atmosphere, carbonizing the PAN nanofiber membrane for 2 to 4 hours at the temperature of 500-800 ℃ in the argon atmosphere, and enabling the flow rate of argon gas to be 30-60 mL/min-1And naturally cooling to room temperature to obtain the carbon nanofiber. And then treating the carbon nanofibers for 200-800 seconds by using a plasma cleaner to obtain the carbon nanofibers which are easy to disperse in water.
(2) Preparation of MXene nanosheet
1 part by mass of LiF was dissolved in 9 mol. L-1Adding 1 part by mass of Ti into HCl under stirring3AlC2And (3) powder. Reacting the obtained mixture at 30-35 ℃ for 20-30 hours to obtain MXene suspension, repeatedly washing the MXene suspension with deionized water, and centrifuging at 3000-5000 rpm for 5-10 minutes until the pH value reaches 6; finally, carrying out ultrasonic treatment on the MXene suspension for 1-2 hours under argon gas flow, wherein the gas flow rate is 30-60 mL/min-1And centrifuging at 3000-5000 rpm for 1-2 hours to obtain a uniform supernatant with MXene tablets. Freezing the MXene nano-sheet, and then freezing and drying the MXene nano-sheet in a freeze dryer to obtain the MXene nano-sheet.
(3) Preparation of carbon nanofiber/MXene composite aerogel
Firstly, according to the mass ratio of the carbon nano fiber to MXene of 1-3: 1 (preferably 1:1) and the mass ratio of the carbon nano fiber to PVP of 2-6: 1 (preferably 4-5:1), dispersing MXene nanosheets in water, then sequentially adding the carbon nano fiber and PVP, and homogenizing for 20-40 minutes at 8000-12000 rpm through a homogenizer to obtain a uniformly dispersed suspension. Subsequently, the dispersion is magnetically stirred for 15 to 30 minutes and ultrasonically treated for 30 to 60 minutes. Then, the copper column is vertically placed in a container filled with liquid nitrogen, a mould with the rest parts being heat-insulated and only the bottom end conducting heat is placed on the copper column, the dispersion liquid is added into the mould placed on the copper column, and when the upper layer of dispersion liquid in the mould is completely frozen, the directional freezing process is finished. And (3) putting the prepared directionally-frozen carbon nanofiber/MXene into a freeze dryer for freeze drying at the temperature of below 50 ℃ below zero and under the pressure of below 20Pa, and drying for more than 48 hours to obtain the carbon nanofiber/MXene composite aerogel.
The prepared aerogel has the directional channel width of 30-60 μm.
As the mass ratio of the carbon nano fiber to MXene is increased from 1:1 to 2:1 and 3:1, the density of the composite aerogel is reduced, and the composite aerogel has ultralow density of 4.87mg cm-3、3.53mg cm-3、2.18mg cm-3。
As the mass ratio of the carbon nanofiber to the MXene was increased from 1:1 to 2:1, 3:1, the composite aerogel had 3%, 9%, and 16% plastic deformation after 500 cycles at 50% strain, respectively, stress retention rates were 96.4%, 74.2%, and 58.3%, respectively, and the maximum compressive strain of the composite aerogel could reach 95% at a mass ratio of the carbon nanofiber to the MXene of 1: 1.
The 3D electrospun carbon nanofiber/MXene composite aerogel can be used as piezoresistive sensor materials.
The invention relates to 2 basic principles:
(1) polyacrylonitrile was chosen as the precursor for carbon fibers because of its high carbon yield and good spinnability.
(2) The addition of the MXene, a two-dimensional material with rich surface active sites, can fully play the synergistic effect of the one-dimensional material and the two-dimensional material to construct the 3D aerogel with a stable structure, solves the problem of interface contact resistance between fibers so that the aerogel has proper conductivity as a sensor material, and endows the aerogel with good elasticity.
Drawings
Fig. 1 is a flow chart of 3D carbon nanofiber/MXene composite aerogel preparation.
Fig. 2 a b is SEM images of side and top views of the 3D carbon nanofiber/MXene composite aerogel prepared in example 5, respectively.
Fig. 3 a b c are digital photographs of the 3D carbon nanofiber/MXene composite aerogel prepared in example 5 before and after compression rebound, respectively.
FIG. 4 a, b and c are the stress-strain curves of the composite aerogels of example 4(CNF/MX-1), example 2(CNF/MX-2) and example 7 (CNF/MX-3), respectively; stress-strain curves for different deformations of the aerogel prepared in example 4; stress-strain curves for 5000 cycles of the aerogel prepared in example 4 at 50% strain; stress-strain curves for different cycles of the aerogel prepared in example 4 at very high strain of 95%.
FIG. 5 a b c d are respective real-time resistance response curves of the aerogel sensor material prepared in example 4 under different strains; sensitivity in the stress range of 0-1 kPa; monitoring different vocal curves of vocal cords of a human body; response and recovery time.
Detailed Description
The present invention will be further described in the following examples, which are illustrative, not restrictive and are not intended to limit the scope of the invention.
Example 1.
Firstly, preparing PAN-based carbon nano-fiber and adding PVP (M)w58000 dissolving in DMF, and adding 8 times the mass of PAN (M)w150000), magnetically stirring to obtain uniform spinning solution, and electrospinning under conditions of receiving distance of 15cm, voltage of 12KV, and electrospinning flow rate of 1mL h-1Grounded aluminum foil was used as the fiber receiver and the received PAN fiber film was vacuum dried at 60 ℃. Then cutting the PAN nanofiber membrane into sheets, pre-oxidizing the PAN nanofiber membrane for 0.5h at 200 ℃ under the air atmosphere, carbonizing the PAN nanofiber membrane for 2h at 500 ℃ under the argon atmosphere, wherein the flow rate of argon gas is 30 mL/min-1And naturally cooling to room temperature to obtain the carbon nanofiber. And then treating the carbon nanofibers for 200s by using a plasma cleaner to obtain the carbon nanofibers which are easy to disperse in water.
Then, MXene nanosheets were prepared by dissolving 1 part by mass of LiF in 9 mol. L-1Adding 1 part by mass of Ti to HCl under stirring3AlC2Powder of. The resulting mixture was reacted at 35 ℃ for 20 hours to give an MXene suspension, which was repeatedly washed with deionized water and centrifuged at 3000rpm for 5 minutes until its pH reached 6. Finally, the MXene suspension was sonicated under argon flow for 1 hour at a gas flow rate of 30mL min-1And centrifuged at 3000rpm for 1 hour to obtain a homogeneous supernatant with MXene pellet. Freezing the MXene nano-sheet, and then freezing and drying the MXene nano-sheet in a freeze dryer to obtain the MXene nano-sheet.
And finally, preparing the carbon nanofiber/MXene composite aerogel, dispersing MXene nanosheets in water according to the mass ratio of 3:1 of CNF to MXene and 2:1 of CNF to PVP, sequentially adding the carbon nanofiber and PVP, and homogenizing at 8000rpm for 20 minutes by a homogenizer to obtain a uniformly dispersed suspension. Subsequently, the dispersion was magnetically stirred for 15 minutes and sonicated for 30 minutes. Then, the copper column is placed in a container filled with liquid nitrogen, a mould which is insulated at the rest part and only has heat conduction at the bottom end is placed on the copper column, the dispersion liquid is added into the mould placed on the copper column, and when the upper layer dispersion liquid in the mould is completely frozen, the directional freezing process is finished. And (3) putting the prepared directionally-frozen carbon nanofiber/MXene into a freeze dryer for freeze drying at the temperature of below 50 ℃ below zero and under the pressure of below 20Pa, and drying for more than 48 hours to obtain the carbon nanofiber/MXene composite aerogel.
The composite aerogel prepared by this example had a directional microchannel structure with a width of 60 μm and a density as low as 2.18mg cm-3. At 50% strain and 10 cycles, the aerogel plastic deformation was at 76% and the stress retention was 26.7%.
Example 2.
The PAN-based carbon nanofiber was prepared in the same manner as in example 1 except that the electrospinning condition was changed to a reception distance of 25cm and a voltage of 20 KV.
MXene nanoplatelets were prepared as in example 1 except that the mixture was reacted at 30 ℃ for 30 hours.
And finally, preparing the carbon nanofiber/MXene composite aerogel, dispersing MXene nanosheets in water according to the mass ratio of 2:1 of CNF to MXene and the mass ratio of 5:1 of CNF to PVP, sequentially adding CNF and PVP, and homogenizing at 10000rpm for 20 minutes by a homogenizer to obtain uniformly dispersed suspension. Subsequently, the dispersion was magnetically stirred for 15 minutes and sonicated for 30 minutes. Then, the copper column is placed in a container containing liquid nitrogen, a mould which is insulated at the rest part and only has heat conduction at the bottom end is placed on the copper column, the dispersion liquid is added into the mould placed on the copper column, and when the upper layer dispersion liquid in the mould is completely frozen, the directional freezing process is finished. And (3) putting the prepared directionally-frozen carbon nanofiber/MXene into a freeze dryer for freeze drying at the temperature of below 50 ℃ below zero and under the pressure of below 20Pa, and drying for more than 48 hours to obtain the carbon nanofiber/MXene composite aerogel.
The composite aerogel prepared by this example had a directional microchannel structure with a width of 40 μm and a density as low as 3.53mg cm-3。
Example 3.
Preparing PAN-based carbon nanofiber and MXene nanosheet, the same as in example 2, and finally preparing CNF/MXene composite aerogel, dispersing the MXene nanosheet in water according to the mass ratio of 2:1 CNF to MXene and 4:1 CNF to PVP, sequentially adding CNF and PVP, and homogenizing at 10000rpm for 20 minutes by a homogenizer to obtain uniformly dispersed suspension. Subsequently, the dispersion was magnetically stirred for 15 minutes and sonicated for 30 minutes. Then, the copper column is placed in a container filled with liquid nitrogen, a mould which is insulated at the rest part and only has heat conduction at the bottom end is placed on the copper column, the dispersion liquid is added into the mould placed on the copper column, and when the upper layer dispersion liquid in the mould is completely frozen, the directional freezing process is finished. And (3) freeze-drying the prepared directionally-frozen carbon nanofiber/MXene in a freeze dryer at the temperature of below 50 ℃ below zero and under the pressure of below 20Pa, and drying for more than 48 hours to obtain the carbon nanofiber/MXene composite aerogel.
The composite aerogel prepared by this example had a plastic deformation of 47% and a stress retention of 54% when strained at 50% and cycled for 10 cycles.
Example 4.
Preparing PAN-based carbon nanofiber and MXene nanosheet, the same as in example 1, and finally preparing CNF/MXene composite aerogel, dispersing the MXene nanosheet in water according to the mass ratio of 1:1 CNF to MXene and 5:1 CNF to PVP, sequentially adding CNF and PVP, and homogenizing at 10000rpm for 20 minutes by a homogenizer to obtain uniformly dispersed suspension. Subsequently, the dispersion was magnetically stirred for 15 minutes and sonicated for 30 minutes. Then, the copper column is placed in a container filled with liquid nitrogen, a mould which is insulated at the rest part and only has heat conduction at the bottom end is placed on the copper column, the dispersion liquid is added into the mould placed on the copper column, and when the upper layer dispersion liquid in the mould is completely frozen, the directional freezing process is finished. And (3) freeze-drying the prepared directionally-frozen carbon nanofiber/MXene in a freeze dryer at the temperature of below 50 ℃ below zero and under the pressure of below 20Pa, and drying for more than 48 hours to obtain the carbon nanofiber/MXene composite aerogel.
The composite aerogel prepared by this example had a directional microchannel structure having a width of 30 μm and a density of 4.87mg cm-3. When the strain is 50% and the cycle is 10 circles, the plastic deformation of the aerogel is only 2%, and the stress retention rate is as high as 99.2%; when the strain is 50% and the cycle is 500 circles, the plastic deformation of the aerogel is only 3.6%, and the stress retention rate reaches 96%; when the strain reaches 50% and the circulation reaches 5000 circles, the aerogel can also maintain the stress retention rate of 91%; at extremely high strain 95%, the aerogel can withstand 500 cycles of compression and the stress retention rate can still reach 70.5%, indicating that the aerogel has super elasticity and excellent mechanical resilience and fatigue resistance, as shown in fig. 4. Thanks to the excellent mechanical resilience of the aerogel, the aerogel sensor has high sensitivity (65 kPa)-1) Ultra low detection limit (<5Pa), fast millisecond response (26ms), large operable strain range (0-95%) and excellent response stability, as shown in fig. 5.
Example 5.
PAN-based carbon nanofibers were prepared as in example 2.
Then, MXene nanosheets were prepared by dissolving 1 part by mass of LiF in 9 mol. L-1Adding 1 part by mass of Ti to HCl under stirring3AlC2And (3) powder. The obtained mixture reacts for 30 hours at 35 ℃ to obtain MXene suspension,it was washed repeatedly with deionized water and centrifuged at 4000rpm for 5 minutes until its pH reached 6. Finally, the MXene suspension was sonicated under argon flow for 1 hour at a gas flow rate of 60mL min-1And centrifuged at 5000rpm for 1 hour to obtain a homogeneous supernatant with MXene pellet. Freezing the MXene nano-sheet, and then freezing and drying the MXene nano-sheet in a freeze dryer to obtain the MXene nano-sheet.
And finally, preparing the CNF/MXene composite aerogel, dispersing MXene nanosheets in water according to the mass ratio of 1:1 of CNF to MXene and 6:1 of CNF to PVP, sequentially adding CNF and PVP, and homogenizing at 12000rpm for 20 minutes by a homogenizer to obtain uniformly dispersed suspension. Subsequently, the dispersion was magnetically stirred for 15 minutes and sonicated for 30 minutes. Then, the copper column is placed in a container filled with liquid nitrogen, a mould which is insulated at the rest part and only has heat conduction at the bottom end is placed on the copper column, the dispersion liquid is added into the mould placed on the copper column, and when the upper layer dispersion liquid in the mould is completely frozen, the directional freezing process is finished. And (3) putting the prepared directionally-frozen carbon nanofiber/MXene into a freeze dryer for freeze drying at the temperature of below 50 ℃ below zero and under the pressure of below 20Pa, and drying for more than 48 hours to obtain the carbon nanofiber/MXene composite aerogel.
Example 6
The PAN-based carbon nanofibers and MXene nanosheets were prepared as in example 5.
And finally, preparing the CNF/MXene composite aerogel, dispersing MXene nanosheets in water according to the mass ratio of 2:1 of CNF to MXene and 4:1 of CNF to PVP, sequentially adding CNF and PVP, and homogenizing at 12000rpm for 20 minutes by a homogenizer to obtain uniformly dispersed suspension. Subsequently, the dispersion was magnetically stirred for 15 minutes and sonicated for 30 minutes. Then, the copper column is placed in a container filled with liquid nitrogen, a mould which is insulated at the rest part and only has heat conduction at the bottom end is placed on the copper column, the dispersion liquid is added into the mould placed on the copper column, and when the upper layer dispersion liquid in the mould is completely frozen, the directional freezing process is finished. And (3) putting the prepared directionally-frozen carbon nanofiber/MXene into a freeze dryer for freeze drying at the temperature of below 50 ℃ below zero and under the pressure of below 20Pa, and drying for more than 48 hours to obtain the carbon nanofiber/MXene composite aerogel.
When the strain of the composite aerogel prepared by the embodiment is 50% and the composite aerogel is cycled for 10 circles, the plastic deformation of the aerogel is only 22%, and the stress retention rate is 68.5%; at 50% strain and 500 cycles, the plastic deformation of the aerogel was only 31% and the stress retention reached 56%. The sensitivity of the aerogel sensor is 15kPa when the load pressure is less than 10Pa-1。
Example 7
Preparing PAN-based carbon nanofiber and MXene nanosheet, the same as in example 5, and finally preparing CNF/MXene composite aerogel, dispersing the MXene nanosheet in water according to the mass ratio of 3:1 CNF to MXene and 5:1 CNF to PVP, sequentially adding CNF and PVP, and homogenizing at 12000rpm for 20 minutes by a homogenizer to obtain uniformly dispersed suspension. Subsequently, the dispersion was magnetically stirred for 15 minutes and sonicated for 30 minutes. Then, the copper column is placed in a container filled with liquid nitrogen, a mould which is insulated at the rest part and only has heat conduction at the bottom end is placed on the copper column, the dispersion liquid is added into the mould placed on the copper column, and when the upper layer dispersion liquid in the mould is completely frozen, the directional freezing process is finished. And (3) freeze-drying the prepared directionally-frozen carbon nanofiber/MXene in a freeze dryer at the temperature of below 50 ℃ below zero and under the pressure of below 20Pa, and drying for more than 48 hours to obtain the carbon nanofiber/MXene composite aerogel.
Example 8.
Firstly, preparing PAN-based carbon nano-fiber and adding PVP (M)w58000 dissolving in DMF, adding 3 times the mass of PAN (M)w150000), magnetically stirring to obtain uniform spinning solution, and electrospinning under the conditions of receiving distance of 20cm, voltage of 20KV and electrospinning flow rate of 1mL h-1Grounded aluminum foil was used as the fiber receiver and the received PAN fiber film was vacuum dried at 60 ℃. Then cutting the PAN nanofiber membrane into sheets, pre-oxidizing the PAN nanofiber membrane for 0.5h at 250 ℃ under the air atmosphere, carbonizing the PAN nanofiber membrane for 2h at 800 ℃ under the argon atmosphere, wherein the flow rate of argon gas is 30 mL/min-1And naturally cooling to room temperature to obtain the carbon nanofiber. Treating the carbon nano-particles with a plasma cleanerAnd (5) obtaining the carbon nano fiber which is easy to disperse in water for 200 s.
The same procedure as in example 2 was used to prepare MXene nanosheets and CNF/MXene composite aerogels.
Example 9.
Firstly, preparing PAN-based carbon nano-fiber and adding PVP (M)w58000 dissolving in DMF, and adding 9 times by mass of PAN (M)w150000), magnetically stirring to obtain uniform spinning solution, and electrospinning under the conditions of receiving distance of 20cm, voltage of 20KV and electrospinning flow rate of 3mL h-1Grounded aluminum foil was used as the fiber receiver and the received PAN fiber film was vacuum dried at 60 ℃. Then cutting the PAN nanofiber membrane into sheets, pre-oxidizing the PAN nanofiber membrane for 1h at 250 ℃ under the air atmosphere, carbonizing the PAN nanofiber membrane for 2h at 600 ℃ under the argon atmosphere, wherein the flow rate of argon gas is 60 mL/min-1And naturally cooling to room temperature to obtain the carbon nanofiber. And then treating the carbon nanofiber for 800s by using a plasma cleaner to obtain the carbon nanofiber which is easy to disperse in water.
The same procedure as in example 2 was used to prepare MXene nanosheets and CNF/MXene composite aerogels.
When the strain of the composite aerogel prepared by the embodiment is 50% and the composite aerogel circulates for 10 circles, the plastic deformation of the aerogel is only 5%, and the stress retention rate is as high as 95.8%; when the strain is 50% and the cycle is 500 circles, the plastic deformation of the aerogel is only 7.6%, and the stress retention rate reaches 92%; at very high strain 95%, the aerogel is able to withstand 500 cycles of compression and the stress retention can still reach 63%. The sensitivity of the aerogel sensor is 37kPa when the load pressure is less than 10Pa-1。

Claims (8)

1. A3D ultra-elastic electrospun carbon nanofiber/MXene composite aerogel collaborative assembly preparation method is characterized by comprising the following steps:
(1) preparation of PAN-based carbon nanofibers
Firstly, dissolving PVP (polyvinyl pyrrolidone) in DMF (dimethyl formamide), adding PAN (polyacrylonitrile) with the mass of 3-9 times, magnetically stirring to obtain uniform spinning solution, and electrospinning under the conditions that the receiving distance is 15-25 cm and the voltage is 12-20 KV respectivelyThe flow rate is 1 mL-5 mL h-1Taking the grounded aluminum foil as a fiber receiver, and drying the received PAN fiber membrane in vacuum; then cutting the PAN nanofiber membrane into sheets, pre-oxidizing the PAN nanofiber membrane for 0.5-2 h at the temperature of 200-250 ℃ in the air atmosphere, carbonizing the PAN nanofiber membrane for 2-4 h at the temperature of 500-800 ℃ in the argon atmosphere, and enabling the flow rate of argon gas to be 30-60 mL/min-1Naturally cooling to room temperature to obtain carbon nanofibers; processing the carbon nanofibers for 200-800 seconds by using a plasma cleaner to obtain carbon nanofibers which are easy to disperse in water;
(2) preparation of MXene nanosheet
1 part by mass of LiF was dissolved in 9 mol. L-1Adding 1 part by mass of Ti into HCl under stirring3AlC2And (3) powder. Reacting the obtained mixture at 30-35 ℃ for 20-30 hours to obtain MXene suspension, repeatedly washing the MXene suspension with deionized water, and centrifuging at 3000-5000 rpm for 5-10 minutes until the pH value reaches 6; finally, carrying out ultrasonic treatment on the MXene suspension for 1-2 hours under argon gas flow, wherein the gas flow rate is 30-60 mL/min-1Centrifuging at 3000-5000 rpm for 1-2 hours to obtain a uniform supernatant with MXene tablets; freezing the MXene nano-sheet, and then freezing and drying the MXene nano-sheet in a freeze dryer to obtain the MXene nano-sheet.
(3) Preparation of carbon nanofiber/MXene composite aerogel
Firstly, according to the mass ratio of the carbon nano fiber to MXene of 1-3: 1 (preferably 1:1) and the mass ratio of the carbon nano fiber to PVP of 2-6: 1 (preferably 4-5:1), dispersing MXene nanosheets in water, then sequentially adding the carbon nano fiber and PVP, and homogenizing for 20-40 minutes at 8000-12000 rpm through a homogenizer to obtain a uniformly dispersed suspension. Subsequently, the dispersion is magnetically stirred for 15 to 30 minutes and ultrasonically treated for 30 to 60 minutes. Then, the copper column is vertically placed in a container filled with liquid nitrogen, a mould with the rest parts insulated and only the bottom end conducting heat is placed on the copper column, the dispersion liquid is added into the mould placed on the copper column, and when the upper layer dispersion liquid in the mould is completely frozen, the directional freezing process is finished. And (3) putting the prepared directionally-frozen carbon nanofiber/MXene into a freeze dryer for freeze drying at the temperature of below 50 ℃ below zero and under the pressure of below 20Pa, and drying for more than 48 hours to obtain the carbon nanofiber/MXene composite aerogel.
2. The method for preparing 3D ultra-elastically electrospun carbon nanofiber/MXene composite aerogel in a synergistic manner according to claim 1, wherein M of PVPw58000, M of PANw＝150000。
3. The 3D ultra-electrospinning carbon nanofiber/MXene composite aerogel collaborative assembly preparation method according to claim 1, wherein the mass ratio of the carbon nanofiber to the MXene is 1:1, and the mass ratio of the carbon nanofiber to the PVP is 4-5: 1.
4. The method for preparing the 3D ultra-electrospinning carbon nanofiber/MXene composite aerogel through synergistic assembly according to claim 1, wherein the prepared aerogel has a directional channel width of 30 μm-60 μm.
5. The method for preparing the 3D ultra-electrospinning carbon nanofiber/MXene composite aerogel in a synergistic manner according to claim 1, wherein the composite aerogel has an ultra-low density of 4.87mg cm as the mass ratio of the carbon nanofiber to the MXene is increased from 1:1 to 2:1 and 3:1 respectively-3、3.53mg cm-3、2.18mg cm-3。
6. The method for preparing the 3D ultra-electrospinning carbon nanofiber/MXene composite aerogel in a synergistic manner according to claim 1, wherein the composite aerogel has 3%, 9% and 16% plastic deformation after 500 cycles under 50% strain and the stress retention rates are 96.4%, 74.2% and 58.3% respectively as the mass ratio of the carbon nanofiber to the MXene is increased from 1:1 to 2:1 and 3:1, and the maximum compressive strain of the composite aerogel can reach 95% when the mass ratio of the carbon nanofiber to the MXene is 1: 1.
7. A3D ultra-electrospun carbon nanofiber/MXene composite aerogel obtainable by the process according to any one of claims 1 to 6.
8. Use of a 3D ultra-electrospun carbon nanofiber/MXene composite aerogel prepared according to the method of any one of claims 1 to 6 as piezoresistive sensor material.
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