CN114854157A - Multifunctional MXene/polyion liquid composite material - Google Patents
Multifunctional MXene/polyion liquid composite material Download PDFInfo
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Abstract
The invention relates to a multifunctional MXene/polyion liquid composite material, and also relates to a preparation method and application of the composite material. The invention compounds the functionalized MXene and the polyion liquid with the self-repairing capability to construct the MXene/polyion liquid composite material with the self-repairing capability and high tensile property, the material has a Janus structure, has asymmetric interface hydrophilicity, acid-base identification capability and good mechanical property, and can respond to tiny strain to generate electrical property change. Therefore, the MXene/polyion liquid composite material is expected to be developed into a pH sensor, a photo-thermal conversion material or a radiation response material, a self-healing flexible wearable sensor and the like, and has wide commercial application prospect.
Description
Technical Field
The invention relates to the field of materials, in particular to an MXene/polyion liquid composite material, and a preparation method and application of the composite material.
Background
MXene is a new class of two-dimensional transition metal carbides, carbonitrides and nitrides for short. Due to the unique structure, large specific surface area, high conductivity and good hydrophilicity, the composite material is widely applied to the fields of batteries, supercapacitors, electromagnetic shielding, water purification, catalysis, biomedicine and the like. MXene has been proven to be an excellent sensing material with high sensitivity and selectivity through a plurality of theoretical researches and experiments. However, its inherent rigidity limits its application in the field of flexible sensors. The composition of the two-dimensional conductive material and the polymer network can improve the electrical property of the polymer network and endow the two-dimensional material with a substrate for space processing and shaping. Meanwhile, compared with an inorganic sensing material, the organic polymer sensing material has the advantages of low density, good biocompatibility, good flexibility, easiness in processing and the like, and has more advantages in the aspects of manufacturing of flexible and wearable electronic products. Polyionic liquids have been widely used as a special organic polymer network in polymer electrolytes, sensors, gas capture and separation, etc. for energy and electrochemical devices. However, no relevant research report is found on the MXene/polyion liquid flexible sensor combining electron conduction and ion conduction.
On the other hand, during the daily use of the sensor, mechanical damage is inevitably caused, resulting in cracks, scratches and even fractures on the surface. Damage to these structures may cause the sensor to lose its proper function. Tongfei Wu et al synthesized a conductive nanocomposite material capable of self-healing by embedding multi-walled carbon nanotubes (MWCNTs) into a self-healing matrix of fatty acid rubber. The composite material shows rapid recovery time (7-10s) and good repeatability in a dynamic pressure sensing test, has 90% of sensitivity at 20kPa, and can be repaired by a press machine after being damaged. The rapid development of the flexible self-healing sensor has great significance to artificial intelligence and intelligent robots. It requires stable mechanical properties, high sensitivity and self-healing sensing materials that are capable of producing a discernible electrical change in response to an external stimulus.
Therefore, development of more novel composite materials is urgently needed.
Disclosure of Invention
The invention aims to provide an MXene/polyion liquid composite material which has good mechanical property, electrical property and self-repairing property, can respond to small strain to generate electrical property change and has super-strong photo-thermal conversion property.
In one aspect of the invention, the invention provides an MXene/polyionic liquid composite material, which comprises MXene and polyionic liquid, wherein the MXene is dispersed in the polyionic liquid, and the content of MXene is 0.1-20 wt% based on the total weight of the composite material.
Preferably, the MXene content is 1 to 15 wt%, for example, 1 wt%, 2 wt%, 3 wt%, 4 wt%, 5 wt%, 6 wt%, 7 wt%, 8 wt%, 9 wt%, 10 wt%, 11 wt%, 12 wt%, 13 wt%, 14 wt%, 15 wt%.
In one embodiment of the invention, the Mxene is aminated. Preferably, the MXene is selected from Ti 3 C 2 T X MXene. Therefore, the MXene is preferably aminated Ti 3 C 2 T X MXene. The interaction of the aminated MXene and the internal hydrogen bond of the polyionic liquid promotes the formation of the composite material.
In the invention, the preparation method of the aminated Mxene comprises the following steps:
MXene powder is dispersed in a dry organic solvent, then an amino coupling agent is added into the solution, the solution is heated for reaction, and after separation, washing and drying are carried out to obtain the aminated Mxene.
Preferably, the organic solvent is at least one selected from the group consisting of alcohols, ethers, esters, aromatic hydrocarbons, acetonitrile, halogenated hydrocarbons, alkanes, and the like, and is preferably at least one selected from the group consisting of methanol, ethanol, diethyl ether, tetrahydrofuran, ethyl acetate, toluene, xylene, acetonitrile, dichloromethane, chloroform, n-hexane, and cyclohexane.
Preferably, the amino coupling agent is selected from aminosilane coupling agents.
More preferably, the amino coupling agent has a structure represented by the following formula 1:
wherein R is 1 -R 3 Each independently selected from: -C1-C6 alkyl, -C1-C2 alkyl-C6-C10 aryl, -C6-C10 aryl;
l is selected from- (CH) 2 ) a -、-(CH 2 ) a NH(CH 2 ) b -；
a is selected from 1, 2, 3, 4, 5 or 6; b is selected from 1, 2, 3, 4, 5 or 6.
Preferably, R 1 -R 3 Each independently selected from: methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, phenyl, benzyl;
l is selected from-CH 2 CH 2 -、-CH 2 CH 2 CH 2 -、-CH 2 CH 2 CH 2 CH 2 -、-CH 2 CH 2 NHCH 2 CH 2 -、-CH 2 CH 2 NHCH 2 CH 2 CH 2 -、-CH 2 CH 2 CH 2 NHCH 2 CH 2 CH 2 -。
Also preferably, the aminosilane coupling agent is selected from the group consisting of 3-Aminopropyltrimethoxysilane (APTES), 3-Aminopropyltriethoxysilane (APTES), N- [3- (trimethoxysilyl) propyl ] Ethylenediamine (EDATMS), and more preferably 3-Aminopropyltriethoxysilane (APTES).
Preferably, the reaction is carried out under the protection of an inert gas atmosphere.
Preferably, the reaction temperature is 60-100 ℃, and preferably 65-85 ℃.
By the above reaction, an amino group can be easily modified on the surface of MXene.
In the present invention, the Mxene may be homemade.
In the present invention, the Ti is 3 C 2 T X MXene can be prepared by selectively etching titanium aluminum carbide (Ti) with LiF/hydrochloric acid (HCl) solution 3 AlC 2 ) Al layer in the powder.
Preferably, the first and second liquid crystal materials are,the Ti 3 C 2 T X The preparation method of MXene comprises the following steps:
stirring LiF and dissolving in hydrochloric acid to obtain Ti 3 AlC 2 Slowly adding the powder into the solution, and stirring at 25-40 ℃ for 12-48 h to etch the Al layer; centrifuging and pouring out the supernatant, then repeatedly washing with deionized water and centrifuging until the pH value of the obtained supernatant is adjusted to 6-6.5; drying the obtained precipitate, dispersing with deionized water, ultrasonic treating in cold water bath under the protection of inert gas atmosphere, centrifuging, collecting the lower precipitate, and drying to obtain Ti 3 C 2 T X MXene。
Wherein the mol ratio of LiF to hydrochloric acid is 1: 3-8, preferably 1: 4-6; the concentration of the hydrochloric acid is 4-12M, preferably 8-11M; LiF and Ti 3 AlC 2 The mass ratio of (A) to (B) is 1-2: 2-1, preferably 1: 1.
in the above preparation method, first, HF is generated in situ in solution by LiF and HCl to etch off Ti 3 AlC 2 An Al layer in (1); furthermore, to avoid the decrease of the material conductivity caused by MXene oxidation, the multi-layer Ti is successfully etched 3 C 2 Ultrasonic treatment of TX MXene in cold water bath under protection of inert gas to break it into Ti with few or even single layer 3 C 2 TX MXene. As the interlayer interaction is weakened, the interlayer gap is increased, and the conductivity of the layered MXene is enhanced.
In one embodiment of the present invention, the polyionic liquid comprises ionic liquid repeating units and (meth) acrylate repeating units in a molecule; the ionic liquid in the ionic liquid repeating unit comprises a cation selected from imidazolium, quaternary ammonium or quaternary phosphonium salts, and an anion.
Preferably, the anion is selected from halide anions (e.g., Cl) - 、Br - Or I - )、BF 4 - 、PF 6 - 、FSI - 、TFSI - 、SbF 6 - 、TfS - At least one of (1).
Preferably, the molar ratio of ionic liquid repeat units to (meth) acrylate repeat units is 1: 1-6, preferably 1: 2 to 4.
Preferably, the polyionic liquid has a structure represented by the following formula 2:
wherein R is selected from hydrogen or methyl;
R a selected from C3-C12 alkyl;
R b selected from C1-C6 alkyl;
X - represents an anion;
n and m represent the number of repeating units.
Preferably, R a Selected from n-butyl, n-pentyl, n-hexyl, isooctyl.
Preferably, R b Selected from methyl, ethyl, isopropyl.
Preferably, X - Selected from halogen anions (e.g. Cl) - 、Br - Or I - )、BF 4 - 、PF 6 - 、FSI - 、TFSI - 、SbF 6 - 、TfS - 。
Preferably, the ratio of n to m is 1: 1-6, preferably 1: 2 to 4.
Preferably, the preparation method of the polyion liquid shown in the formula 2 comprises the following steps:
carrying out copolymerization reaction on 1-vinyl imidazole and alkyl (meth) acrylate in the presence of an initiator to obtain a copolymer, dissolving the copolymer in an organic solvent, adding halogenated C3-C12 alkane, heating and stirring for reaction, and optionally carrying out ion exchange to obtain the polyion liquid.
Preferably, the molar ratio of 1-vinylimidazole to alkyl (meth) acrylate is 1: 1-6, preferably 1: 2 to 4. The molar ratio of the 1-vinyl imidazole to the halogenated C3-C12 alkane is 1:1 to 1.5, preferably 1:1 to 1.2.
Preferably, the alkyl (meth) acrylate is at least one selected from the group consisting of methyl acrylate, ethyl acrylate, isopropyl acrylate, methyl methacrylate, ethyl methacrylate, and isopropyl methacrylate.
Preferably, in the halogenated C3-C12 alkane, the halogenated means being substituted by chlorine, bromine or iodine. Further preferably, the halogenated C3-C12 alkane is selected from at least one of n-butyl bromide, n-pentane bromide, n-hexane bromide and isooctane bromide.
Preferably, the ion exchange means exchanging halogen ions for BF 4 - 、PF 6 - 、FSI - 、TFSI - 、SbF 6 - 、TfS - At least one of (1). The ion exchange is a conventional step in the preparation of ionic liquids and can be carried out by a person skilled in the art using conventional methods.
In the invention, the MXene/polyion liquid composite material can have a film form, namely an MXene/polyion liquid composite film.
Preferably, the thickness of the MXene/polyion liquid composite membrane is 10-500 μm, preferably 50-300 μm.
Preferably, the MXene/polyion liquid composite material is a Janus material.
In the composite material, in particular the composite film, the content of MXene is higher on one side of the film than on the other side. Preferably, 60% or more of the MXene is distributed within a range of 60% from the film thickness on the film side. More preferably, 70% or more, or 80% or more, or 90% or more, or 95% or more of the MXene is distributed in a range of 60% (preferably 55%, more preferably 50%) of the film thickness from the film side.
In a preferred embodiment of the present invention, the method for preparing the MXene/polyion liquid composite material comprises:
quantitatively weighing MXene and polyion liquid, dissolving the polyion liquid in an organic solvent, adding MXene under stirring, then ultrasonically dispersing in a cold water bath, and drying the prepared suspension to obtain the MXene/polyion liquid composite material.
Preferably, the suspension is poured into a mould for drying; or the suspension is coated on a substrate and dried.
Preferably, the drying is carried out at a temperature below 50 ℃ (or below 40 ℃), preferably at room temperature; the drying is optionally carried out under reduced pressure.
Preferably, the organic solvent is at least one selected from the group consisting of alcohols, ethers, esters, acetonitrile, halogenated hydrocarbons, and the like, and is preferably at least one selected from the group consisting of methanol, ethanol, diethyl ether, tetrahydrofuran, ethyl acetate, acetonitrile, dichloromethane, and chloroform.
Preferably, the volume mass ratio of the organic solvent to the polyion liquid is 2-10ml/g, preferably 4-7 ml/g.
Preparation of
In another aspect of the present invention, the present invention provides a preparation method of the MXene/polyion liquid composite material, comprising:
quantitatively weighing MXene and polyion liquid, dissolving the polyion liquid in an organic solvent, adding MXene under stirring, then ultrasonically dispersing in a cold water bath, and drying the prepared suspension to obtain the MXene/polyion liquid composite material.
Preferably, the suspension is poured into a mould for drying; or the suspension is coated on a substrate and dried.
Preferably, the drying is carried out at a temperature below 50 ℃ (or below 40 ℃), preferably at room temperature; the drying is optionally carried out under reduced pressure.
Preferably, the organic solvent is at least one selected from the group consisting of alcohols, ethers, esters, acetonitrile, halogenated hydrocarbons, and the like, and is preferably at least one selected from the group consisting of methanol, ethanol, diethyl ether, tetrahydrofuran, ethyl acetate, acetonitrile, dichloromethane, and chloroform.
Preferably, the volume mass ratio of the organic solvent to the polyion liquid is 2-10ml/g, preferably 4-7 ml/g.
The preparation method of the Mxene and the polyionic liquid can be as described in the specification, so that the Mxene and the polyionic liquid can be prepared by the method described in the specification.
Therefore, the invention provides a preparation method of the MXene/polyion liquid composite material, which comprises the following steps:
step 1. preparation of Ti 3 C 2 T X MXene
Stirring LiF and dissolving in hydrochloric acid to obtain Ti 3 AlC 2 Slowly adding the powder into the solution, and stirring for 12-48 h at 25-40 ℃ to etch the Al layer; centrifuging and pouring out the supernatant, then repeatedly washing with deionized water and centrifuging until the pH value of the obtained supernatant is adjusted to 6-6.5; drying the obtained precipitate, dispersing with deionized water, ultrasonic treating in cold water bath under the protection of inert gas atmosphere, centrifuging, collecting the lower precipitate, and drying to obtain Ti 3 C 2 T X MXene；
Mixing Ti 3 C 2 T X MXene powder is dispersed in dry organic solvent, then amino coupling agent is added into the solution, heating reaction is carried out, and after separation, washing and drying are carried out to obtain aminated Ti 3 C 2 T X Mxene；
Carrying out copolymerization reaction on 1-vinyl imidazole and alkyl (meth) acrylate in the presence of an initiator to obtain a copolymer, dissolving the copolymer in an organic solvent, adding halogenated C3-C12 alkane, heating and stirring for reaction, and optionally carrying out ion exchange to obtain polyion liquid;
Quantitative weighing of aminated Ti 3 C 2 T X The MXene/polyion liquid composite material is prepared by dissolving polyion liquid in an organic solvent, adding MXene under stirring, performing ultrasonic dispersion in a cold water bath, and drying the prepared suspension to obtain the MXene/polyion liquid composite material.
Wherein each step may be preferably a protocol as herein before described.
In the present invention, the inert gas is at least one selected from nitrogen and argon.
Performance and application
The MXene/polyion liquid composite material of the invention belongs to composite materials combining electronic conduction and ionic conduction, and comprises Ti 3 C 2 T X MXene functionalized flake and polyionic liquid. The MXene content has a certain difference between the front surface and the back surface of the film due to the sedimentation of MXene in the film forming process, and the MXene content is a Janus material. The MXene/polyion liquid composite material has very ideal properties.
The invention discovers that the MXene/polyion liquid composite material has different MXene contents on two sides, so that the hydrophilic degree of the two sides of the membrane is changed, the water contact angle of one side with high MXene content is smaller than that of the other side, and the hydrophilicity is better. The performance of difference in water contact angle can promote the MXene/polyion liquid composite material to be applied to certain related fields such as oil-water interfaces.
In addition, the MXene/polyion liquid composite material has different response behaviors to different pH values. Under an acidic environment, the MXene/polyion liquid composite material can be coiled; specifically, the fibers are curled toward the side with low MXene content. When transferred to neutral or alkaline solutions, the crimped material slowly unfolds. Meanwhile, the MXene/polyion liquid composite material is in a spreading state when being in a neutral or alkaline solution.
Therefore, the invention provides an application of the MXene/polyion liquid composite material as a pH sensor.
In another aspect, the invention also provides a pH sensor made of an MXene/polyion liquid composite material.
Under the irradiation of near-infrared laser, MXene can convert light energy into heat energy to be released, and is a material with high photo-thermal conversion efficiency, and the photo-thermal conversion efficiency can reach 50% as reported in the literature. Therefore, the performance of the MXene/polyion liquid composite material in terms of photo-thermal conversion effect is observed, and the MXene/polyion liquid composite material is found to have excellent photo-thermal conversion effect and can show change in apparent morphology within a short few seconds of laser radiation such as near infrared laser radiation. Therefore, the MXene/polyion liquid composite material is expected to be developed into a photo-thermal conversion material and a radiation response material. For example, the area of the composite material can be controlled during the manufacturing process to have a portion of the composite material and a portion of the pure PIL, thereby achieving a driving change of the material in the near infrared scene.
Therefore, the invention provides the application of the MXene/polyion liquid composite material as a photo-thermal conversion material; in addition, the invention also provides application of the MXene/polyion liquid composite material as a radiation response material, and preferably, the material can respond to near infrared stimulation.
On the other hand, the invention also provides a photothermal conversion material which is prepared from the MXene/polyion liquid composite material; the invention also provides a radiation response material which is made of MXene/polyion liquid composite material, preferably, the material can respond to near infrared stimulation.
The MXene/polyion liquid composite material has good flexibility, can bear spiral and torsional deformation without any fracture and deformation, and the deformed material can be continuously flattened into a long strip in an initial state and can be repeatedly folded and bent for multiple times and then unfolded into the initial state; meanwhile, the MXene/polyion liquid composite material has excellent tensile property, so that the MXene/polyion liquid composite material is a flexible material with good mechanical property.
Meanwhile, the MXene/polyion liquid composite material has a good self-repairing effect, mainly comes from the interaction of anions and cations in the substrate polyion liquid, and meanwhile, the introduction of amino promotes the hydrogen bond interaction between the MXene modified by the amino and the polyion liquid. In addition, due to the conductivity of MXene, the MXene/polyion liquid composite material has good electrical properties, and the resistance value can be adjusted through the content of MXene.
The MXene/polyion liquid composite material can respond to tiny strain to generate electrical property change so as to output an electrical signal, and therefore the MXene/polyion liquid composite material can be used as a strain sensor. By combining the good mechanical property, electrical property and self-repairing property of the MXene/polyion liquid composite material, the MXene/polyion liquid composite material is expected to be developed into a flexible strain sensor, particularly a self-repairing flexible strain sensor such as a flexible electronic skin.
Therefore, the invention provides the application of the MXene/polyion liquid composite material as a flexible strain sensor, in particular to a self-repairing flexible strain sensor.
The invention also provides a flexible strain sensor, in particular a self-repairing flexible strain sensor, which is made of the MXene/poly ionic liquid composite material.
Preferably, the flexible strain sensor is a flexible electronic skin.
The invention has the following advantages:
the invention prepares the multilayer Ti with less surface defects and good conductivity by selecting a proper etching method 3 C 2 T X MXene, and dispersed into small-layer and single-layer sheet Ti 3 C 2 T X MXene. Forming a thin sheet of Ti 3 C 2 T X The MXene is compounded with the polyion liquid with the self-repairing capability after being functionalized, so that an MXene/polyion liquid composite material with the self-repairing capability and high tensile property is constructed, and a flexible sensor prepared from the material can generate obvious signal change for tiny deformation such as knocking and the like; can be worn on the finger to detect the bending motion of the finger. The MXene deposition during the drying process causes the MXene/polyion liquid composite material to have a unique Janus structure, shows the change of the degree of hydrophilicity of two sides and has certain pH response. The material also shows an ultra-strong photo-thermal conversion effect, and can be heated to more than 70 ℃ within 8 s. The internal ionic and hydrogen bonding interactions ensure that damage can be repaired at 60 ℃. Therefore, the MXene/polyion liquid composite material is expected to be developed into a pH sensor, a photo-thermal conversion material or a radiation response material, a self-healing flexible wearable sensor and the like, and has the advantages ofHas wide commercial application prospect.
Drawings
The accompanying drawings, which are included to provide a further understanding of the invention and are incorporated in and constitute a part of this specification, illustrate embodiments of the invention and together with the description serve to explain the principles of the invention and not to limit the invention. In the drawings:
FIG. 1: thin layer and single layer MXene and MXene-NH 2 The preparation process of (1).
FIG. 2: (a) ti 3 AlC 2 Infrared spectroscopy of MXene; (b) MXene-NH 2 And the infrared spectrum of 3-aminopropyltriethylsilane.
FIG. 3: (a) XRD curves of MXene and MAX phases; (b) XPS spectra of MXene.
FIG. 4: (a) an unetched MAX phase material; (b) ti after etching and after ultrasonic stripping 3 C 2 T X 。
FIG. 5: and (3) a preparation process of the flexible sensor.
FIG. 6: (a) front SEM image of PIL film. (b) Back side SEM image of PIL film. (c) MXene-NH 2 @ PIL film front SEM image. (d) MXene-NH 2 @ PIL film backside SEM image.
FIG. 7: schematic diagram of deposition process.
FIG. 8: (a) 2 wt.% (e), 4 wt.%, 6 wt.%, 8 wt.%, 10 wt.% MXene-NH 2 Cross-sectional view of @ PIL film (arrow length MXene-NH in the figure) 2 The layer thicknesses were 26.2. mu.m, 37.4. mu.m, 50.5. mu.m, 64.8. mu.m, and 112.5. mu.m) in this order. (f)10 wt% MXene-NH 2 The cross-sectional view of the @ PIL film contains MXene moieties.
FIG. 9: MXene-NH 2 @ PIL.
FIG. 10: (a) PIL is in solution at pH 4, pH 7 and pH 13. (b) MXene-NH2@ PIL was in solution at pH 4, pH 7 and pH 13.
FIG. 11: MXene-NH 2 @ PIL.
FIG. 12: MXene-NH 2 A real object diagram of the MXene @ PIL flexible sensor under the conditions of initial, bending, torsion and spiral.
FIG. 13: MXene-NH 2 @ PIL tensile curve.
FIG. 14: MXene-NH 2 The photothermal conversion of @ PIL under 808nm laser is schematically shown.
FIG. 15: MXene-NH 2 And @ PIL is a photo-thermal conversion physical diagram under the laser of 808 nm.
FIG. 16: MXene-NH 2 @ PIL photothermal conversion curve under 808nm laser.
FIG. 17: (a) MXene-NH 2 @ PIL self-repairing real object diagram. (b) MXene-NH 2 @ PIL self-repair SEM image.
FIG. 18: MXene-NH 2 A graph of the self-healing mechanism of @ PIL.
FIG. 19: (a) MXene-NH 2 The content is related to the resistance. (b) Resistance values before and after self-repair change.
FIG. 20: (a) and knocking the practical picture of the experiment. (b)10 wt% MXene-NH 2 @ PIL the relative resistance of the coil during tapping changes. (c)10 wt% MXene-NH 2 @ PIL real-time current change during tapping.
FIG. 21: (a) photograph of the finger joint bent by 30 deg.. (b)10 wt% MXene-NH 2 The relative resistance change of the @ PIL material during bending 30 °. (c)10 wt% MXene-NH 2 @ PIL material real-time current change during 30 ° bending.
Detailed Description
The preferred embodiments of the present invention will be described in conjunction with the accompanying drawings, and it will be understood that they are described herein for the purpose of illustration and explanation and not limitation.
Raw materials and reagents
1-Vinylimidazole (VI, 99%) and azobisisobutyronitrile (AIBN, 98%) were purchased from Shanghai Arlatin Biotech Ltd. Ethyl acrylate (EA, 99%), lithium fluoride (LiF, 99.8%), n-butyl bromide (C) 4 H 9 Br, > 99%), ethyl acetate from shanghai mclin biochemistry science co. 3-aminopropyltriethoxysilane (APTES, 98%) was purchased from Bailingwei technologies, Inc., Beijing. Dichloromethane, petroleum ether, anhydrous methanol, lithium bistrifluoromethanesulfonimide (LiTFSI, 99.5%) obtained from Michelle laboratory facilitiesA company. Concentrated hydrochloric acid (HCl, 36.5%), anhydrous ether were purchased from Guanghong chemical industries, Beijing. Ti 3 AlC 2 The powder (400 mesh) was purchased from Jiangsu Xiancheng nanomaterial science and technology limited. All reagents and starting materials were used without further purification.
Instrumentation and testing
1. Fourier transform infrared spectroscopy (FTIR): BRUKER sensor II with the test range of 4000-400 cm -1 ；
2. Nuclear magnetic resonance spectrum (NMR): JEOL JNM-ECZS400, 400MHz, solvent CDCl 3 And DMSO-d 6 Internal standard Tetramethylsilane (TMS);
3. scanning Electron Microscope (SEM): hitachi SU8000, accelerating voltage of 5.0kV, accelerating current of 10 muA, and observing a sample after spraying gold;
x-ray diffractometer (XRD): rigaku Smartlab with a test voltage of 45.0kV, a current of 200.0mA, and an X-ray wavelength of
(Cu-Kalpha) at a scan rate of 5 deg. min -1 The scanning range is 10-80 degrees;
5. thermogravimetric analyzer (TGA): SDT Q600 Instrument at N 2 Heating to 600 deg.C at a heating rate of 10 deg.C/min under atmosphere;
6. differential Scanning Calorimeter (DSC): TA Instruments DSC 250Instrument, N 2 Under the atmosphere, heating from room temperature to 180 ℃ at the speed of 10 ℃/min, then cooling to-50 ℃ at the speed of 10 ℃/min, and then heating to 180 ℃ at the speed of 10 ℃/min;
7. universal testing machine: instron 5967, the stretching speed is 0.1 mm/s;
x-ray photoelectron spectroscopy (XPS): ULVCA-PHI Inc., PHI-5000 Versaprobe;
9. an electrochemical workstation: morning CHI 660B;
10. source table: keysight, B2910 BL;
11. a multimeter: zhengtai electric, CHNT-ZTY 0103A;
12. a single lens reflex camera: canon, EOS 5D Mark IV 5D 4.
Example 1: preparation and characterization of MXene flakes and amination
The MXene flakes were prepared as shown in figure 1.
1、Ti 3 C 2 T X Preparation of MXene sheet
LiF (1g) was first dissolved in hydrochloric acid (9M, 20mL) and stirred at room temperature for 30 min. Then, 1g of Ti 3 AlC 2 The powder was slowly added to the above solution (within 5 min) and stirred in a water bath at 35 ℃ for 24h to etch the Al layer. Subsequently, centrifugation was performed at 3500rpm for 10min, and the supernatant was decanted, followed by repeated washing with deionized water and centrifugation several times until the pH of the resulting supernatant was adjusted to 6. The obtained precipitate was dried at 50 ℃ for 12 h. And then dispersing the dried powder with 200mL of deionized water, carrying out ultrasonic treatment in a cold water bath for 1h under the protection of nitrogen atmosphere, and centrifuging at 10000rpm for 10 min. Finally, collecting the lower layer precipitate, and drying at 50 ℃ for 12h to obtain Ti 3 C 2 T X MXene sheet.
2、Ti 3 C 2 T X Amination of MXene sheet
1g of Ti prepared as described above was taken 3 C 2 T X MXene was dispersed in 75mL of dry toluene solvent, and then APTES (0.75mL) was added dropwise to the solution, stirred under nitrogen for 30min and then heated to 80 ℃ and the solution refluxed overnight. Washed by toluene and methanol, centrifuged and dried in vacuum at 50 ℃ for 24h to obtain aminated Ti 3 C 2 T X MXene(MXene-NH 2 ) A sheet.
3. Characterization of
By IR spectroscopy on Ti 3 C 2 T X The structure of MXene was characterized and the results are shown in FIG. 2 a. At 3680cm -1 And 1050cm -1 Two very distinct characteristic peaks at (A) are due to stretching vibration of-OH group, and at 1404cm -1 The characteristic peak of (A) shows C-F stretching vibration. In contrast to unetched Ti 3 AlC 2 The etched MXene surface is enriched with a large number of-OH, -F and other groups, which shows that Ti 3 C 2 T X MXene had been well etched. For MXene-NH 2 Infrared characterization was performed and the results are shown in fig. 2 b. 2900cm -1 The characteristic peak near the position corresponds to the stretching vibration of methylene in APTES, 3600cm -1 The characteristic peak is due to-NH 2 Caused by stretching vibration at 1090cm -1 And 730cm -1 The distinct characteristic peaks shown there correspond to the asymmetric and symmetric stretching vibrations of Si-O-Si. The appearance of the above characteristic peak indicates that APTES is successfully grafted to the surface of MXene, MXene-NH 2 The synthesis of (2) was successful.
Further, Ti was verified by a combination of X-ray diffraction (XRD) and X-ray photoelectron spectroscopy (XPS) 3 C 2 T X Etching of MXene. Before and after etching, Ti as shown in FIG. 3a 3 AlC 2 (002) The peak was reduced from 9.5 to 6.36, and the shift of the (002) peak was due to the removal of Ti by etching 3 AlC 2 Medium Al layer and in Ti 3 C 2 T X The surface of the material is introduced with end groups such as-F and-OH. Another indication of successful etching is Ti 3 AlC 2 The peak at 39 ° is greatly reduced (fig. 3 a). XPS Spectroscopy (FIG. 3b) for characterization of synthesized Ti 3 C 2 T X The surface chemistry of MXene. The peaks observed at 290eV, 531eV and 687eV are assigned to C1s, O1 s and F1s, respectively, and the characteristic peaks at 459eV and 563eV correspond to Ti 2p and Ti 2s, respectively. This indicates that Ti is present 3 AlC 2 Etched Ti 3 C 2 T X MXene has the surface with end groups of-O, -OH and-F, which is consistent with the test result of XRD.
Ti was observed by Scanning Electron Microscope (SEM) 3 AlC 2 Micro-morphology before and after etching. Unetched Ti 3 AlC 2 The closely stacked layered structure (fig. 4a) is present, and the stacked layered structure is very unfavorable for the conduction of electrons between holes, which easily causes the conductive performance of the material to be greatly reduced. And etched Ti 3 C 2 T X Presenting an accordion-like multilayer structure (fig. 4b left). The weakening of the interlayer interaction opens the gaps between the laminae, which facilitates the intercalation of the intercalant and provides conditions for subsequent ultrasonic dispersion into few layers and a single layer of MXene.After ultrasonication, successful release of the monolayer MXene flakes as shown on the right of FIG. 4b, the interlaminar interaction was destroyed by the ultrasonication and the multiple MXene layers were dispersed into a monolayer MXene flake, but the ultrasonication did not guarantee one hundred percent dispersion of the multiple MXene layers into a monolayer MXene flake and some minor MXene flakes were present. From the SEM image, the size of the single-layer MXene flake is about 8-10 μm, but the size is not uniform, and the flake with smaller or even nanometer size can be obtained, and the small-size structure ensures good dispersibility and stability of MXene in various solvents and is also beneficial to being coated by the PIL segment.
Example 2: MXene-NH 2 Preparation and characterization of @ PIL flexible sensor
MXene-NH 2 The process for making the @ PIL flexible sensor is shown in FIG. 5.
1. Preparation of PVI/TFSI-co-PEA (PIL)
0.94g (10.0mmol) of VI, 3.00g (30.0mmol) of EA, AIBN (30mg,0.183mmol) and DMF (10mL) were uniformly mixed in a flask and stirred at 65 ℃ for 24 hours under a nitrogen atmosphere. Then, after ether precipitation, the mixture is dried in vacuum to obtain the light yellow solid PVI-co-PEA copolymer. Next, 1.5g of PVI-co-PEA was dissolved in methanol, and n-butyl bromide (10.0mmol, 1.37g) was added and reacted at 60 ℃ for 12 hours under a nitrogen atmosphere. After the reaction was completed, most of the methanol was removed by rotary evaporation, precipitated in petroleum ether/ethyl acetate (1:1, v/v), and dried under vacuum at 80 ℃ to give a pale yellow solid (PVI/Br-co-PEA).
PVI/Br-co-PEA (3.47g) copolymer was dissolved in methanol and then the PVI/Br-co-PEA solution was added dropwise to a 0.1mol/L solution of LiTFSI in methanol. After stirring for 72h, the ions were exchanged thoroughly, and then the excess LiTFSI was removed by repeated precipitation in water after rotary evaporation of the bulk of the solvent. The precipitate was further dried under vacuum at 100 ℃ for 12h to give the product PVI/TFSI-co-PEA (PIL).
2、MXene-NH 2 Preparation of @ PIL
0.9g of PIL was weighed out and dissolved in a methanol solution (5mL), and 0.1g of MXene-NH was added while stirring 2 And then ultrasonically dispersed in a cold water bath. Ultrasonic treatment for 30minMXene-NH 2 Fully mixed in the PIL solution to successfully prepare 10 wt% MXene-NH 2 @ PIL suspension. Based on the same method, different MXene-NH are prepared 2 Mass fraction MXene-NH 2 @ PIL sample. Mixing MXene-NH 2 The @ PIL suspension is poured into a polytetrafluoroethylene mold and dried at room temperature to obtain MXene-NH 2 @ PIL film.
3. Characterization of
The front and back views of the pure PIL film are smooth (FIGS. 6a, 6b), while MXene-NH 2 @ PIL differs significantly from the surface of the PIL film. MXene-NH on film front side (FIG. 6c) 2 The content is significantly less than the content of the back side of the film (fig. 6 d). This is due to the presence of MXene-NH during the film formation process 2 Resulting in MXene-NH (FIG. 7) 2 The content is different between the front and back of the film. However, as can be readily seen from FIG. 6, most of MXene-NH, whether the front or back side 2 Can be well mixed and coated by PIL, and has partial exposed MXene-NH 2 The sheet is present. Further, different MXene-NH pairs were examined by SEM 2 Mass fraction MXene-NH 2 The cross-sectional morphology of the @ PIL film was characterized (fig. 8). As can be seen from FIGS. 8a-e, with MXene-NH 2 The content of MXene-NH deposited in the lower layer is gradually increased 2 The thickness of (2) is increased.
The special composite structure has certain advantages, namely MXene-NH 2 The flakes are protected by a PIL coating, which avoids MXene-NH 2 MXene-NH can be prolonged by direct contact of the flakes with air, causing oxidation thereof in a hot and humid environment 2 The @ PIL material has the advantages of long service life and durability, and stable electrical property and tensile property of the sensor. Simultaneous exposure of MXene-NH 2 The flakes can be joined outside the PIL into conductive microelectronic pathways, MXene-NH, when strain occurs 2 When the @ PIL sensor is bent, the micro-channel inside the sensor can be broken and cracked slightly, so that the electrical performance is changed, a small current is changed, and the effect of responding to small deformation is achieved.
Example 3: performance test
1、MXene-NH 2 Water contact Angle test of @ PIL
Due to MXene-NH 2 The uneven distribution of the front and back sides of the membrane material may lead to a certain difference in the properties of the front and back sides of the membrane, and the membrane with different properties on both sides is called a Janus membrane in research. For Janus type MXene-NH 2 The hydrophilicity of both sides of the @ PIL membrane was tested (figure 9). As can be seen, the contact angles on both the front and back sides are less than 90 degrees (75.6 degrees on the front and 60.6 degrees on the back). But because of the back-deposited MXene-NH 2 The higher content results in a lower water contact angle on the back side than on the front side, which is more hydrophilic than the front side.
2. Janus type MXene-NH 2 Ph responsiveness study of @ PIL membranes
As shown in fig. 10, no macroscopic changes were observed when the plain PIL film was immersed in solutions of different acid-base environments. However, this is in contrast to MXene-NH in pH 7 solution 2 The @ PIL material was spread and when immersed in an acidic solution with pH 4, the film immediately contracted and rolled up in a straight direction (fig. 10b, left); subsequently, MXene-NH 2 When @ PIL is transferred to an alkaline solution having a pH of 7 or 13, MXene-NH is compressed 2 @ PIL will slowly unfold. This phenomenon was found to be not reproducible during the experiment, probably due to MXene-NH under acidic conditions 2 The amino group in (b) reacts with an acid, while in an alkaline solution, the ester group is largely hydrolyzed under alkaline conditions to cause structural damage.
3、MXene-NH 2 Content pair MXene-NH 2 Study on influence of glass transition temperature of @ PIL film
MXene-NH was studied by DSC 2 The effect of the content on the glass transition temperature of the conductive composite is shown in table 1 and fig. 11. When MXene-NH 2 When the content was increased from 0% to 2% to 10% by weight, the Tg was increased from 11.75 ℃ to 39.98 ℃ and then decreased to 27.66 ℃ and thereafter increased to 33.88 ℃. This may be due to MXene-NH 2 When the content is gradually increased, MXene-NH 2 The increased hydrogen bonding interaction with PIL leads to a decrease in Tg, but MXene-NH 2 Content (wt.)When the amount is further increased, an excessive amount of the filler is accumulated to make the composite material rigid, and thus the Tg starts to increase.
TABLE 1 different MXene-NH 2 Content of MXene-NH 2 @ PIL Tg summary.
4、MXene-NH 2 Mechanics Property determination of @ PIL
The mechanical property is an important index for evaluating the performance of the flexible material. MXene-NH prepared as shown in FIG. 12 2 The @ PIL material can bear spiral deformation and torsional deformation, even 180-degree bending deformation without any fracture and deformation, even the deformed material can be continuously flattened into a long strip shape in an initial state, and can be repeatedly folded, bent and then unfolded into the initial state for multiple times. The excellent appearance of the prepared flexible sensor undoubtedly proves the great potential of the flexible PIL applied to the ideal wearable flexible sensor.
In addition, for different MXene-NH 2 The samples of the contents were subjected to stress-strain tests, and the results are shown in fig. 13. MXene-NH as compared to tensile Curve of undoped Polymer alone 2 The tensile strength of the material is improved visually by adding the compound, and MXene-NH in the material is shown 2 Interaction with the PIL may enhance the tensile properties of the material. When MXene-NH 2 When the content was increased from 2 wt% to 10 wt%, the tensile strain was decreased from 160% to 80% and then increased to 170%. The tensile strength decreased to 8.2MPa after increasing from 8.3MPa to 11.6MPa, contrary to the trend of tensile strain. When MXene-NH 2 After a content of more than 4%, the tensile strength starts to decrease significantly. 4 wt% MXene-NH 2 The tensile strength of @ PIL can reach 11.6 MPa. This indicates that the increase in tensile strength is not only related to the filling of the material on the micrometer scale, but also to MXene-NH 2 And hydrogen bonding interactions between PILs. When MXene-NH 2 At contents exceeding 4 wt%, the tensile strength of the material decreases sharply. This may be because too much filler makes the composite material rigid, therebyBut a part of the mechanical properties are lost. Although MXene-NH 2 The higher content of the compound reduces the tensile strength of the material, but the tensile strain as a whole becomes better, and the tensile strength is not lower than 7MPa, and the excellent tensile property is still obtained.
5、MXene-NH 2 Test of photothermal conversion Effect of @ PIL
MXene-NH 2 Photothermal testing of @ PIL is shown in FIG. 14. Mixing different MXene-NH 2 The content of the film was placed under a near infrared laser at 808nm with the power density set at 1.5w/cm 2 The temperature change of the film under the laser is recorded by a thermal imaging camera, and the reading is carried out once every half second, wherein the content of MXene-NH is one 2 The @ PIL material was tested at least three times and the average was plotted. As shown in fig. 15, MXene-NH was left under laser off conditions 2 @ PIL remains upright, but MXene-NH after the laser is turned on 2 @ PIL melts the bend quickly. In a short 8s period, different MXene-NH 2 The specimens in the amount can be rapidly warmed up from room temperature to above 70 ℃ and even the specimens can be fused (table 2). And with MXene-NH 2 The increase of the content of @ PIL obviously improves the photothermal conversion effect. 10 wt% MXene-NH 2 The @ PIL material can even be warmed to 93 deg.c over a period of 8s (fig. 16).
TABLE 2 different MXene-NH 2 Content of MXene-NH 2 The photothermal conversion effect of @ PIL.
6、MXene-NH 2 Self-healing Properties of @ PIL
With 10 wt% MXene-NH 2 Content of MXene-NH 2 The self-repairing performance of the material is studied by taking the material of @ PIL as an example. Preparing a sample into a long strip shape (figure 17a), cutting off the sample in the middle, splicing the sample together, heating the sample at 60 ℃ for 3 hours, and connecting two broken ends together well to achieve the self-repairing effect; the sample strips after self-repairing can not break even if the sample strips are hung on a weight of 10g, and the self-repairing effect is good. For the microscopic scale of the repair siteMorphology, observed with SEM, is shown in fig. 17 b. As can be seen from the figure, the damage after the self-repair basically disappears, the damaged part before the self-repair can only be barely distinguished in the image, and when the repaired wound is enlarged, the surface of the wound is found to be uneven, which is caused by the fall caused during splicing. While the normally spliced aligned sections return to substantially a full plane. Meanwhile, in order to evaluate whether the conductive composite material can be used as an electronic device after being damaged and repaired, the resistance values of the material before and after self-healing are measured. 10 wt% MXene-NH 2 The sample @ PIL exhibited a good self-repairing effect even though the resistance was changed to some extent after the complete cut and repair of the resistance (fig. 19 b). As shown in FIG. 18, MXene-NH 2 The good self-repairing effect of the @ PIL material is mainly derived from the interaction of anions and cations in the substrate PIL, but the introduction of amino promotes MXene-NH 2 With the PIL, MXene-NH is promoted by the two internal forces 2 The @ PIL material shows a good self-repairing effect, and can repair damage and restore the original properties and functions in a short time.
7、MXene-NH 2 Resistance test of @ PIL
The quality of the electrical properties of the conductive composite is very important. Measuring MXene-NH with different contents by using a multimeter 2 MXene-NH of 2 @ PIL resistance value of sample. As shown in FIG. 19a, MXene itself has excellent conductivity to make MXene-NH 2 The resistance value of the @ PIL composite material follows MXene-NH 2 The content is increased and decreased, but the content does not show regular decrease. Although MXene-NH 2 The increase of the content can enhance the conductivity of the material, but can also reduce the tensile property of the material, so that 10 wt% MXene-NH is selected to meet the requirement of a proper sensor material 2 The @ PIL composite material is used for subsequent sensing performance test. 10 wt% MXene-NH 2 The resistance value of the @ PIL composite material is 6400 omega.
8、MXene-NH 2 @ PIL strain sensing characteristic
Whether the flexible sensor can generate the electrical property change for the micro strainAnd thus outputs an electrical signal, which is crucial for flexible sensors. For MXene-NH 2 The sensory performance of the @ PIL composite material is tested, and MXene-NH is observed 2 The response of the @ PIL material to minute strains. Selecting 10 wt% MXene-NH 2 The material @ PIL was fixed to both ends of the jig, and the material was gently tapped with a finger, and then the finger was released, and this operation was repeated a plurality of times to observe changes in the output electrical signal (fig. 20 a). As shown in FIGS. 20b and 20c, the real-time I-T curve clearly shows 10 wt% MXene-NH 2 The @ PIL material captures the sensitivity of micro-deformations. When the sample was pressed regularly by a finger, the stress state of the conductive composite material was changed, and there was a clear regular change in the current (fig. 20 c).
For flexible electronic skin application, 10 wt% MXene-NH 2 The @ PIL material was fixed at the joints of the fingers, the fingers were gently bent to 30 °, then straightened, and the same action was repeated to observe the change in the output electrical signal (fig. 21 a). As shown in FIGS. 21b and 21c, the real-time I-T curve clearly shows 10 wt% MXene-NH 2 @ PIL is a sensitive capture of such minute deformations as 30 ° of finger bending. When the finger was bent at 30 ° regularly and recovered and the stress-strain state of the conductive composite was changed, the current showed a distinct regular change (fig. 21 c).
It will be apparent to those skilled in the art that various changes and modifications may be made in the present invention without departing from the spirit and scope of the invention. Thus, if such modifications and variations of the present invention fall within the scope of the claims of the present invention and their equivalents, the present invention is also intended to include such modifications and variations.
Claims (10)
1. An MXene/polyion liquid composite material comprises MXene and polyion liquid, wherein the MXene is dispersed in the polyion liquid, and the content of the MXene is 0.1-20 wt% based on the total weight of the composite material.
2. The composite of claim 1, wherein Mxene is aminated; preferably, the MXene is preferablyBeing aminated Ti 3 C 2 T X MXene。
3. The composite material of claim 1, wherein the aminated Mxene is prepared by a process comprising:
MXene powder is dispersed in a dry organic solvent, then an amino coupling agent is added into the solution, the solution is heated for reaction, and after separation, washing and drying are carried out to obtain the aminated Mxene.
4. The composite material of claim 1, wherein the polyionic liquid comprises ionic liquid repeating units and (meth) acrylate repeating units in a molecule; the ionic liquid in the ionic liquid repeating unit comprises a cation selected from imidazolium, quaternary ammonium or quaternary phosphonium salts and an anion; preferably, the molar ratio of ionic liquid repeat units to (meth) acrylate repeat units is 1: 1-6, preferably 1: 2 to 4.
5. The composite material of claim 4, wherein the polyionic liquid has a structure represented by formula 2 below:
wherein R is selected from hydrogen or methyl;
R a selected from C3-C12 alkyl;
R b selected from C1-C6 alkyl;
X - represents an anion;
n and m represent the number of repeating units.
6. The composite material of claim 5, wherein the polyion liquid shown in formula 2 is prepared by a method comprising:
carrying out copolymerization reaction on 1-vinyl imidazole and alkyl (meth) acrylate in the presence of an initiator to obtain a copolymer, dissolving the copolymer in an organic solvent, adding halogenated C3-C12 alkane, heating and stirring for reaction, and optionally carrying out ion exchange to obtain the polyion liquid.
7. Composite material according to claim 1, characterized in that it is a composite film in which the content of MXene is higher on one side of the film than on the other side; preferably, 60% or more of the MXene is distributed in a range of 60% from the film thickness on the film side; more preferably, 70% or more, or 80% or more, or 90% or more, or 95% or more of the MXene is distributed in a range of 60% (preferably 55%, more preferably 50%) of the film thickness from the film side.
8. A method of preparing the MXene/polyionic liquid composite of claim 1, comprising:
quantitatively weighing MXene and polyion liquid, dissolving the polyion liquid in an organic solvent, adding MXene under stirring, then ultrasonically dispersing in a cold water bath, and drying the prepared suspension to obtain the MXene/polyion liquid composite material.
9. Use of the MXene/polyion liquid composite according to claim 1 as a pH sensor, a light-to-heat conversion material, a radiation responsive material or a flexible strain sensor.
10. A pH sensor, a photothermal conversion material, a radiation responsive material, or a flexible strain sensor made from the MXene/polyionic liquid composite material of any one of claims 1-5.
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