CN111595363A - MXene/printing ink high-sensitivity sensor without high-valence metal ions and preparation method thereof - Google Patents
MXene/printing ink high-sensitivity sensor without high-valence metal ions and preparation method thereof Download PDFInfo
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- CN111595363A CN111595363A CN202010572032.4A CN202010572032A CN111595363A CN 111595363 A CN111595363 A CN 111595363A CN 202010572032 A CN202010572032 A CN 202010572032A CN 111595363 A CN111595363 A CN 111595363A
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01D—MEASURING NOT SPECIALLY ADAPTED FOR A SPECIFIC VARIABLE; ARRANGEMENTS FOR MEASURING TWO OR MORE VARIABLES NOT COVERED IN A SINGLE OTHER SUBCLASS; TARIFF METERING APPARATUS; MEASURING OR TESTING NOT OTHERWISE PROVIDED FOR
- G01D5/00—Mechanical means for transferring the output of a sensing member; Means for converting the output of a sensing member to another variable where the form or nature of the sensing member does not constrain the means for converting; Transducers not specially adapted for a specific variable
- G01D5/12—Mechanical means for transferring the output of a sensing member; Means for converting the output of a sensing member to another variable where the form or nature of the sensing member does not constrain the means for converting; Transducers not specially adapted for a specific variable using electric or magnetic means
- G01D5/14—Mechanical means for transferring the output of a sensing member; Means for converting the output of a sensing member to another variable where the form or nature of the sensing member does not constrain the means for converting; Transducers not specially adapted for a specific variable using electric or magnetic means influencing the magnitude of a current or voltage
- G01D5/16—Mechanical means for transferring the output of a sensing member; Means for converting the output of a sensing member to another variable where the form or nature of the sensing member does not constrain the means for converting; Transducers not specially adapted for a specific variable using electric or magnetic means influencing the magnitude of a current or voltage by varying resistance
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
- B41F—PRINTING MACHINES OR PRESSES
- B41F15/00—Screen printers
- B41F15/08—Machines
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
- B41F—PRINTING MACHINES OR PRESSES
- B41F15/00—Screen printers
- B41F15/14—Details
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
- B41F—PRINTING MACHINES OR PRESSES
- B41F16/00—Transfer printing apparatus
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
- B41J—TYPEWRITERS; SELECTIVE PRINTING MECHANISMS, i.e. MECHANISMS PRINTING OTHERWISE THAN FROM A FORME; CORRECTION OF TYPOGRAPHICAL ERRORS
- B41J29/00—Details of, or accessories for, typewriters or selective printing mechanisms not otherwise provided for
- B41J29/38—Drives, motors, controls or automatic cut-off devices for the entire printing mechanism
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D11/00—Inks
- C09D11/02—Printing inks
- C09D11/03—Printing inks characterised by features other than the chemical nature of the binder
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D11/00—Inks
- C09D11/30—Inkjet printing inks
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D11/00—Inks
- C09D11/30—Inkjet printing inks
- C09D11/38—Inkjet printing inks characterised by non-macromolecular additives other than solvents, pigments or dyes
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01B—MEASURING LENGTH, THICKNESS OR SIMILAR LINEAR DIMENSIONS; MEASURING ANGLES; MEASURING AREAS; MEASURING IRREGULARITIES OF SURFACES OR CONTOURS
- G01B7/00—Measuring arrangements characterised by the use of electric or magnetic techniques
- G01B7/16—Measuring arrangements characterised by the use of electric or magnetic techniques for measuring the deformation in a solid, e.g. by resistance strain gauge
- G01B7/18—Measuring arrangements characterised by the use of electric or magnetic techniques for measuring the deformation in a solid, e.g. by resistance strain gauge using change in resistance
- G01B7/20—Measuring arrangements characterised by the use of electric or magnetic techniques for measuring the deformation in a solid, e.g. by resistance strain gauge using change in resistance formed by printed-circuit technique
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01K—MEASURING TEMPERATURE; MEASURING QUANTITY OF HEAT; THERMALLY-SENSITIVE ELEMENTS NOT OTHERWISE PROVIDED FOR
- G01K7/00—Measuring temperature based on the use of electric or magnetic elements directly sensitive to heat ; Power supply therefor, e.g. using thermoelectric elements
- G01K7/16—Measuring temperature based on the use of electric or magnetic elements directly sensitive to heat ; Power supply therefor, e.g. using thermoelectric elements using resistive elements
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01L—MEASURING FORCE, STRESS, TORQUE, WORK, MECHANICAL POWER, MECHANICAL EFFICIENCY, OR FLUID PRESSURE
- G01L1/00—Measuring force or stress, in general
- G01L1/18—Measuring force or stress, in general using properties of piezo-resistive materials, i.e. materials of which the ohmic resistance varies according to changes in magnitude or direction of force applied to the material
Abstract
The invention belongs to the technical field of sensors, and relates to an MXene/printing ink high-sensitivity sensor without high-valence metal ions and a preparation method thereof. The sensor provided by the invention takes an MXene/ink composite structure as a sensing active component, does not contain high-valence metal ions except for MXene materials, and is characterized in that MXene nanosheets with small sizes are dispersed in ink through preparing a dispersion liquid and a dispersion process to form an MXene sensing network in the ink, so that the sensing sensitivity of the sensing active component can be greatly improved. Through a special dispersing process, the dispersing effect which can be achieved by adding high-valence metal ions can be achieved, and the problems caused by the high-valence metal ions are avoided. The MXene/ink high-sensitivity sensor can be conveniently coated on a test base material or the surface of a substrate through a simple forming mode (screen printing, thermal transfer printing, printer jet forming and the like), the design method of a complex sensing array is simplified, the influence of high-valence metal ions on a sensing network is avoided, and the monitoring accuracy is enhanced.
Description
Technical Field
The invention belongs to the technical field of sensors, and particularly relates to an MXene/ink high-sensitivity sensor without high-valence metal ions and a preparation method thereof.
Background
The composite material becomes an important structural material in many advanced fields due to excellent mechanical properties of the composite material. The detection of the structural integrity of the composite material and the prediction of the remaining life of the test piece can avoid sudden failure of the composite material. Strain gauges and fiber optic sensors are currently widely used in various areas of engineering for critical infrastructure monitoring and damage detection, but they may also form defects in composite structures, leading to cracks and damage to the composite components. Therefore, there is a need to develop new techniques to monitor the damage status of composite structures.
Two-dimensional materials have attracted extensive attention due to their unique electrical, magnetic, and optical properties for their wide application in a wide variety of fields. Two-dimensional materials which are synthesized at present comprise graphene, molybdenum disulfide, boron carbide, tungsten disulfide, silylene and the like, and a novel transition metal carbide MXene is prepared from Yury Gogotsi in 2011 by a chemical etching method. MXene conforms to the general formula MnAXn-1Wherein "M" usually represents transition metal (Ti, V, Zn, etc.), "a" is mainly group iii or IV element (Al, Si, etc.), "X" is C or N element, MXene has not only characteristics of large specific surface area, many active sites and unique "accordion" layered structure, etc., but also advantages of excellent hydrophilicity, metal conductivity, good thermal dispersion property, etc., and has wide application as capacitive energy storage material, electromagnetic shielding material, etc., but application as sensor is rarely mentioned.
Patent CN109238522A proposes a wearable flexible stress sensor, which contains two-dimensional inorganic nanosheet material and ink, wherein the two-dimensional inorganic nanosheet material includes graphene oxide and MXene material. But the composition also comprises high-valence metal ions and a high-molecular chelating agent, the ink containing the metal ions usually contains the chelating agent, the high-molecular chelating agent has the capability of selectively forming chelate for the high-valence metal ions with different valence states and different geometric configurations, and can form a water-soluble complex for the polyvalent metal ions in a quite wide pH value range, and the water-soluble complex and the high-molecular chelating agent are matched with each other, so that the MXene material also has an excellent dispersing effect. However, Cu2+、Fe3+The high-valence metal ions have strong oxidizability, MXene is also easy to oxidize, the possibility of oxidizing MXene is increased, the conductivity of MXene after oxidation is greatly reduced, so that the sensitivity of the manufactured sensor is reduced, meanwhile, other conductive ions can be introduced to play a role in constructing a sensor network, the stability of the sensor is reduced, and the analysis of experimental results is inaccurate.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides an MXene/ink high-sensitivity sensor without high-valence metal ions and a preparation method thereof, wherein an MXene material has excellent conductivity, high sensitivity and wide strain range, and MXene nanosheets with small sizes are dispersed in ink by optimizing the concentration and dispersion process of MXene to form an MXene sensing network in the ink, so that the sensing sensitivity of a sensing active component can be greatly improved. By adjusting the mass ratio of MXene to ink, the sensitivity of the sensor can be adjusted. By optimizing the dispersion process and parameters, the MXene2-5 layer few-layer dispersion can be realized, the mixing degree with the printing ink is high, the high conductivity and the dispersibility can be achieved without a high-molecular chelating agent and high-valence metal ions, and compared with a sensor containing metal ions, the sensor is more stable in performance and higher in sensitivity. Meanwhile, the less the components in the ink, the less the performance impact on the MXene/ink composite, and the more beneficial it is to coat in different ways. The invention provides another idea for uniformly dispersing MXene, solves the problems of influence on the sensitivity and data accuracy of a sensor caused by high-valence metal ions, and solves the problems of influence on the properties of ink, such as viscosity increase and the like caused by addition of a high-molecular chelating agent and the high-valence metal ions. The MXene/ink high-sensitivity sensor without high-valence metal ions can be directly coated on the surface of a test base material through various forming modes (screen printing, thermal transfer printing and printer spray forming), and the problems that the traditional sensor needs to be embedded in the test base material for structural health monitoring and forms structural defects on materials are solved.
In order to achieve the purpose, the invention adopts the following technical scheme:
one aspect of the present invention is to provide an MXene/ink high sensitivity sensor without high valence metal ions, wherein the sensing active component of the sensor is a composite structure of MXene material and ink having excellent conductivity, high sensitivity and wide strain range, wherein MXene can be completely dispersed in the ink, and the composite material does not contain high valence metal ions except for the MXene material. As a further preferred aspect of the present invention, the MXene material is obtained by selectively etching the MAX phase of the matrix material with hydrochloric acid and lithium fluoride; in the MAX phase of the parent phase material, M is transition metal, A is mainly III group element or IV group element, and X is C element or N element; the MXene material has a size of about 200-500 nm.
The parent phase material is preferably Ti3AlC2The MXene material is preferably Ti3C2。
The ink can be solvent type ink, water-soluble ink and UV ink, does not contain high-valence metal ions and chelating agents, is preferably solvent type ink, contains a small amount of aromatic hydrocarbon solvent, and is favorable for blending with MXene dispersion liquid.
As a further preferred aspect of the present invention, in the MXene/ink composite structure, the ratio of the mass of the MXene to the mass of the ink is 1: (1 to 100), preferably 1: 25.
the resistance value corresponding to the sensing active component of the MXene/ink high-sensitivity sensor can change when the external force condition or the temperature condition of the sensor changes, and the MXene/ink with different mass ratios has different sensitivities to the external force response.
Preferably, the MXene/ink high-sensitivity sensor provided by the invention is a piezoresistive sensor, a strain sensor or a temperature sensor, and the size of the sensor is 10mm multiplied by (10-30) mm.
Preferably, the MXene/ink high-sensitivity sensor provided by the invention is used by coating the MXene/ink composite material on the surface of a test substrate.
Preferably, the test substrate applied to the MXene/ink high-sensitivity sensor provided by the invention is a composite material, metal, ceramic or plastic.
According to another aspect of the present invention, there is provided a method for preparing an MXene/ink high sensitivity sensor coated on a surface of a test substrate, comprising the steps of:
step (1): the MXene powder is dispersed in a dispersion solvent to prepare MXene dispersion liquid, and in order to ensure that MXene can be completely dispersed in the ink without depending on a polymer chelating agent and metal ions, a dispersion process for preparing the dispersion liquid comprises the following steps: stirring MXene materials in a dispersion solvent, performing ultrasonic dispersion treatment, centrifuging at the rotating speed of 3000r/min, and removing impurities in the solution; repeating the stirring, ultrasonic dispersion treatment, centrifuging and impurity removal dispersion processes for 3-5 times, gradually reducing the ultrasonic dispersion power within the range of 100-50W in each time to prepare MXene dispersion liquid, and adding the dispersion liquid into the ink according to a required proportion;
step (2): uniformly mixing the MXene/ink mixture obtained in the step (1) through a dispersion process, and removing a dispersion solvent to obtain an MXene/ink composite material;
and (3): coating the prepared MXene/printing ink composite material on a test base material or the surface of a substrate, and curing;
and (4): and respectively connecting one ends of two wires to two ends of the surface of the MXene/printing ink composite material, coating conductive silver paste to bond the wires and the MXene/printing ink composite material, drying the conductive silver paste, and connecting the other ends of the two wires to the signal conversion element.
The stirring process in the step (1) is preferably magnetic stirring for 10-30 min, and the ultrasonic dispersion treatment process is preferably 10-20 min. The gradual dispersion can improve the dispersion effect by multiple times of dispersion without depending on a dispersing agent, and the dispersion parameter is changed each time to avoid damage to an MXene lamellar structure after long-time dispersion treatment and influence on the sensing effect. The number of dispersions varies depending on the dispersion solvent, the first stage being intended to disperse MXene present in the powder in lumps, the second stage being intended to disperse MXene in the dispersion solution (to avoid that in the first stage the lumps of MXene are not dispersed in the dispersion solution), the latter stages being intended to obtain a more homogeneous MXene dispersion.
The centrifugal rotating speed in the step (1) is preferably 3000r/min, the time is 10min, partial blocky MXene and unreacted MXene in the preparation process can form fluffy precipitate according to different MXene qualities in the centrifugal impurity removal process, the fluffy precipitate is attached to the bottom of a centrifugal tube, then the bottom of the centrifugal tube is removed, a small amount of impurities can be prevented from being brought out in the process of taking out the upper-layer dispersion liquid through multiple times of centrifugation, and the impurities can be effectively removed through multiple times of centrifugation treatment with unchanged centrifugation speed.
According to the type of the selected ink, the dispersion solvent can be selected from toluene, water, acetone and dimethyl sulfoxide (DMSO), dimethyl sulfoxide is preferred, MXene has excellent dispersibility in dimethyl sulfoxide, and the organic solvent has good compatibility with the ink and can eliminate the harm of aromatic hydrocarbon in the ink to human bodies.
As a further preferred of the present invention, the dispersing process in the step (2) is one of mechanical grinding dispersion, ultrasonic dispersion or addition of a dispersing agent; the method for removing the dispersion solvent in the step (2) is one of a vacuum drying method, a freeze-drying method or a molecular sieve method.
The MXene/DMSO dispersion solution is added into the ink, and is uniformly dispersed and mixed by magnetic stirring and ultrasonic, and then the mixture is dried in vacuum. The magnetic stirring time for mixing the dispersion in the ink is preferably 2 hours, and the rotating speed is 400rpm to 700rpm, preferably 500 rpm. The ultrasonic dispersion time is 20min, and the power is 70W-90W, preferably 80W.
In a further preferred embodiment of the present invention, the drying temperature of the vacuum drying method is 60 ℃ and the drying time is 1 hour.
Preferably, the method for coating the MXene/ink composite material in the step (3) is one of screen printing, thermal transfer printing or printer spray forming,
as a preferable example of the method of coating an MXene/ink composite in the step (3), there is provided a method of detecting by printing the MXene/ink composite on the surface of the composite. The method comprises the following specific steps:
step (1): preparing MXene/printing ink composite material and putting into an injector;
step (2): placing the cured composite sheet on a printer sheet;
and (3): printing the MXene/ink composite material on a composite material plate by a printer to form a conductive network;
and (4): and curing the composite plate with the conductive nanocomposite material to enable the composite plate and the conductive nanocomposite material to be mutually bonded.
In a further preferred embodiment of the method, the printer is formed by injection molding.
As a further preference of the method, MXene/ink composite is filled into a syringe under vacuum to avoid the generation of bubbles
As a further preferred method, the MXene/ink composite material is injected onto the composite material plate through a nozzle with the thickness of 0.4-0.6 mm. And the moving speed of the syringe cannot exceed 4 mm/sec.
As a further preferred method, the size of the sensor active member to be printed is 10mm × 10mm to 10mm × 30 mm.
As a further optimization of the method, the composite plate with the MXene/printing ink composite material is cured under the vacuum condition, the curing temperature is 60 ℃, and the curing time is 2 hours.
The invention has the beneficial effects that:
(1) the MXene/ink high-sensitivity sensor does not contain high-valence metal ions, wherein the MXene material has excellent conductivity, high sensitivity and a wide strain range, and MXene nanosheets with small sizes are dispersed in the ink by optimizing the concentration and the dispersion process of MXene to form an MXene sensing network in the ink, so that the sensing sensitivity of a sensing active component can be greatly improved. The MXene conductivity can not be reduced due to the fact that no high-valence metal ions are contained, so that the sensing sensitivity of the sensing active component is improved, in addition, the MXene conductivity can not be reduced due to the fact that no high-valence metal ions are contained, the influence factor that the high-valence metal ions participate in construction of the sensing network can be avoided, the sensor is more stable, and the monitoring accuracy is improved.
(2) By adjusting the mass ratio of MXene to printing ink, the sensitivity of the sensor can be adjusted, and piezoresistive sensors, strain sensors or temperature sensors meeting different requirements and environments can be prepared.
(3) The traditional sensor needs to be embedded in a composite material for structural health monitoring, and the MXene/ink high-sensitivity sensor without high-valence metal ions can be conveniently coated on the surface of a test base material in different forming modes, particularly the existing ink printing modes such as screen printing, thermal transfer printing, printer spray forming and the like, so that structural defects are not formed on the material.
Drawings
FIG. 1 is a flow chart of MXene/ink composite preparation.
Fig. 2 is a scanning electron microscope image of MXene after corrosion.
Fig. 3 is a polarizing microscope image of MXene dispersed in DMSO.
Fig. 4 is a transmission electron micrograph of MXene/ink.
Fig. 5 shows the MXene infrared spectrum and raman spectrum after stripping.
FIG. 6 is a drawing graph of the MXene/ink sensor (MXene ink mass ratio 1: 25) prepared in example 1.
FIG. 7 is a graph of the stretch curves of MXene/ink sensors (mass ratio of 1:25 and 1:5) in different mass ratios in examples 1 and 3.
FIG. 8 is a graph of the stepped loading and unloading curves for MXene/ink sensors (mass ratio of 1:75 and 1:5) at low strain for examples 2 and 3.
Fig. 9 is a graph of the MXene/ink sensor response to temperature for example 4.
Fig. 10 is a graph of the monitoring of the MXene/ink sensor versus the metal pressure vessel of example 4.
FIG. 11 is a drawing graph showing the tensile strength of the MXene/ink sensor (MXene ink mass ratio 1: 25) prepared in comparative example 7, to which a high valent metal ion was added.
FIG. 12 shows the dispersion of MXene in DMSO in different stages of dispersion in example 8.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is described in further detail below with reference to the accompanying drawings and embodiments. The specific embodiments described herein are merely illustrative of the invention and do not delimit the invention. In addition, the technical features involved in the embodiments of the present invention described below may be combined with each other as long as they do not conflict with each other.
The MXene/printing ink is used as an active material of the sensor, the sensor and a lead are bonded by coating conductive silver paste on an electrode, and the response of the sensor to an external force is represented by a signal acquired by a resistance acquisition unit.
As an example of the invention, MXene material adopts HC1 and LiF to selectively etch the A layer in the mother phase MAX, and hydrated lithium ions are intercalated, and then a single-layer MXene nanosheet is obtained through centrifugation and vacuum drying. Then MXene powder is dispersed in DMSO, then the ink is mixed with MXene dispersion liquid, magnetic stirring and ultrasonic dispersion are carried out, and after vacuum drying for one hour, the MXene/ink composite material is obtained. And the MXene/ink-based high-sensitivity sensor is prepared by printing on the surface of the composite material sprayed with the MXene/ink. When the composite material is under the action of tensile force, the contact area between MXene and the nanosheets in the ink is reduced, the tunneling distance is prolonged, the current transmission is difficult, the resistance is increased sharply, and higher sensitivity is obtained. Sensors of different mass ratios respond differently to force. The sensor is more sensitive near the percolation threshold.
In order to reduce the cost for preparing the sensor, as shown in fig. 1, a solution blending method is adopted to mix MXene dispersion liquid with printing ink, magnetic stirring and ultrasonic dispersion are carried out, and the MXene/printing ink composite material is prepared after vacuum drying.
An example of a specific synthesis step for MXene is: 5g of MAX powder was slowly added to 100ml of a 9M hydrochloric acid and 5g of LiF mixed solution, and reacted for 24 hours at room temperature under magnetic stirring. Research shows that when the molar ratio of LiF to MAX is 7.5: 1 and the hydrochloric acid concentration is 9M, the obtained MXene lamella has the best quality and higher yield. Then, the mixed solution is subjected to centrifugal cleaning (3500rpm) until the pH value reaches neutral, MXene is fluffy after the last centrifugation, the centrifugal speed is adjusted to 1500rpm, and the centrifugation is continued to take the upper-layer blend for removing impurities in the MXene. The collected blend was then centrifuged l h at 3500rpm to separate the blend into a supernatant and a slurry, which was dried in a vacuum oven at 60 ℃ to yield the desired MXene powder.
MXene has good hydrophilicity and conductivity, and the dispersion liquid of MXene in water has obvious tyndall effect. As shown in fig. 2, which is a scanning electron microscope image of MXene after etching, MXene synthesized by etching is generally nano-sized and still has a complete enlarged structure. MXene is smaller in size than other two-dimensional materials and is more easily dispersed in the ink to avoid oxidation in air.
Specific synthesis steps of MXene/ink are exemplified by: weighing 0.1g of MXene powder, immersing 2g of DMSO in the MXene powder, adding MXene into the DMSO, magnetically stirring for 30min, ultrasonically dispersing the mixed solution for 10min, and centrifuging (rotating speed of 3000r/min) for 20min to remove impurities. The steps of stirring, ultrasonic dispersion, centrifugation and impurity removal are repeated for three times, and the ultrasonic power is respectively 100W, 90W and 80W. Adding the ink with a proper proportion, stirring for 1h by magnetic force, carrying out 80W ultrasonic treatment for 20min to completely disperse MXene in DMSO, weighing 1g of the ink, adding the ink into the dispersion, carrying out ultrasonic dispersion for 20min after 2h of magnetic stirring, and drying the MXene/ink in a vacuum drying oven at 60 ℃ for 1 h.
The method in which the dispersion is dispersed in the ink may be replaced by other dispersion means such as mechanical milling dispersion and addition of a dispersant, and the method of removing the dispersant may be replaced by other means such as freeze drying or molecular sieve.
As shown in fig. 3, the dispersion of MXene in DMSO was observed using a polarization microscope. It can be seen that the spacing between MXene is about 300nm and the dispersibility is good. As shown in FIG. 4, the transmission electron microscope image of MXene/ink shows that the ink is attached to the surface of the MXene nanosheet layer, and the classification phenomenon of MXene and ink is obvious.
Infrared and Raman analyses of exfoliated lamellar MXene are shown in FIG. 5, 3857, 3754 and 2922cm-1The absorption band of (a) is mainly related to hydroxyl groups; 2290 and 2067cm-1The absorption band of (a) is hydrogen bonded due to the presence of oxygen; 1742 and 1632cm-1The absorption band of (a) is associated with a C ═ O bond; 1371cm-1The absorption band at (a) is associated with hydrogen bonding because of the presence of molecular water (O-H). The infrared spectrum and Raman spectrum results show that the MXene surface contains a large amount of oxygen and hydroxyl groups, so that the hydrophilicity of the MXene surface is enhanced, the MXene surface can be used for water-based ink, and the solvent is deionized water; the aqueous phase can also be prepared by self-emulsificationFunctional groups are introduced into the resin, the UV ink contains 40% of the host resin and 40% of the monomer, and MXene can be introduced into the resin by an organic solvent such as acetone toluene.
The present invention will be described in further detail with reference to the following examples, which are intended to illustrate the present invention in further detail and are not intended to limit the scope of the present invention.
Example 1
Weighing 0.1g of MXene powder, immersing 2g of DMSO in the MXene powder, adding MXene into the DMSO, magnetically stirring for 30min, ultrasonically dispersing the mixed solution for 10min, and centrifuging (rotating speed of 3000r/min) for 20min to remove impurities. The steps of stirring, ultrasonic dispersion, centrifugation and impurity removal are repeated for three times, the ultrasonic power is respectively 100W, 90W and 80W, MXene is completely dispersed in DMSO, 2.5g of solvent-based ink without high-valence metal ions is weighed and added into the dispersion liquid, the solvent-based ink is stirred magnetically for 2 hours and then is dispersed ultrasonically for 20 minutes, and the MXene/ink is placed into a vacuum drying oven to be dried for 1 hour at the temperature of 60 ℃. The mass ratio of MXene to ink was 1: 25.
The prepared MXene/ink composite was placed into a syringe, after which the cured composite board was placed on a printer board, which printed MXene/ink onto the composite board at a speed of no more than 4 mm/sec, measuring 10mm by 30 mm. And curing the MXene/ink to enable the MXene/ink to be mutually adhered to the composite material plate, connecting wires at two ends of the MXene/ink composite material, coating conductive silver paste for fixation, connecting the other ends of the wires to a resistance collector, and carrying out a graded loading and unloading test on a to-be-tested piece under the conditions of mechanical tensile test inspection and micro strain (0-0.06%).
Example 2
The mass of the ink was changed to 7.5g, the ratio of MXene to the mass of the ink was 1:75, and the rest was the same as in example 1.
Example 3
The mass of the ink was changed to 0.5g, the ratio of MXene to the mass of the ink was 1:5, and the rest was the same as in example 1.
Example 4
The MXene/ink composite was prepared as in example 1.
The preparation method of the MXene/ink sensor comprises the following steps: the prepared MXene/ink composite material is printed on a flexible circuit by a thermal transfer printing method, and the size of the flexible circuit is 10mm multiplied by 10mm to form a sensor array. The flexible circuit is connected to the metal pressure vessel by welding, and the response of the sensor to temperature is collected by using a resistance collector and a thermocouple, as shown in fig. 9. And 3000 times of pressurizing and pressure releasing tests are carried out on the pressure container, and the service condition of the sensor in multiple use is detected, as shown in fig. 10.
Example 5
Weighing 0.1g of MXene powder, immersing 2g of water in the MXene powder, magnetically stirring for 30min, ultrasonically dispersing the mixed solution for 10min, and centrifuging (rotating speed of 3000r/min) for 20min to remove impurities. The steps of stirring, ultrasonic dispersion, centrifugation and impurity removal are repeated for four times, the ultrasonic power is respectively 90W, 80W, 70W and 60W to ensure that MXene is completely dispersed in water, 5g of water-soluble ink without high-valence metal ions is weighed and added into the dispersion liquid, the water-soluble ink is magnetically stirred for dispersion after a dispersant is added, and the MXene/ink is put into a freeze dryer to be dried at-40 ℃ for overnight. The mass ratio of MXene to ink was 1: 50.
Printing the prepared MXene/printing ink composite material on the surface of a ceramic plate in a screen printing mode, wherein the size of the MXene/printing ink composite material is 10mm multiplied by 20mm, connecting a wire to two ends of the MXene/printing ink composite material after the printing ink is solidified, coating conductive silver paste on the two ends of the MXene/printing ink composite material to fix the wire, and connecting the other end of the wire to a signal conversion element. The manufactured sensor can be used as a temperature sensor and a strain sensor for detecting the thermal shock resistance and the thermal shock fracture mechanism of the ceramic at the same time.
Example 6
Weighing 2g of MXene powder, immersing 40g of acetone into the MXene powder, magnetically stirring for 30min, ultrasonically dispersing the mixed solution for 10min, and centrifuging (rotating speed of 3000r/min) for 20min to remove impurities. The steps of stirring, ultrasonic dispersion, centrifugation and impurity removal are repeated for five times, and the ultrasonic power is respectively 90W, 80W, 70W, 60W and 50W. MXene was completely dispersed in toluene, 120g of UV ink containing no high-valent metal ion was weighed and added to the dispersion, and dispersed in a mill disperser for 4 hours, and MXene/ink was dried in a vacuum oven at 60 ℃ for 1 hour. The mass ratio of MXene to ink was 1: 60.
Comparative example 7
0.02g of chitosan was added to the dispersion, stirred for 24 hours, and 0.002g of Fe was added thereto before the ink was added to the dispersion3+And stirred for 5 hours to completely disperse MXene in DMSO, otherwise the same as in example 1.
Example 8
Stirring MXene material in DMSO for 20min, performing ultrasonic dispersion treatment for 20min, centrifuging at a rotation speed of 3000r/min, and removing impurities in the solution; repeating the dispersion processes of stirring, ultrasonic dispersion treatment, centrifugation and impurity removal for 5 times, gradually decreasing the ultrasonic dispersion power within the range of 100W-60W at intervals of 10W in each time to prepare MXene dispersion liquid, and observing the dispersion liquid after each treatment by using a polarization microscope.
The prepared MXene/ink composite was placed into a syringe, after which the plastic plate was placed on a printer plate, and the MXene/ink was printed onto the plastic plate at a speed not exceeding 4 mm/sec, with dimensions of 10mm by 30 mm. And then curing the MXene/ink composite material to enable the MXene/ink composite material and the MXene/ink composite material to be mutually bonded, connecting the conducting wires to two ends of the MXene/ink composite material, coating conductive silver paste to fix the conducting wires, and connecting the other ends of the conducting wires to the signal conversion element. The manufactured sensor can be used for detecting the strength, plasticity, fatigue limit and the like of plastics.
FIG. 6 shows the stress-strain curve of MXene/ink (mass ratio of 1: 25) in example 1 for measuring tensile property of composite material, and the sensitivity of the sensor can be measured by using the mathematical expression GF ═ (Δ R/R)0) And/means the ratio of the rate of change of resistance to strain, with a sensor being more sensitive with larger values of GF. It can be seen that the sensor maintains ultra high sensitivity at 116.6 and 554.3 respectively at different stages of stretching, and the fit of this value is very high, reaching 0.992 and 0.996.
FIG. 7 shows the stress-strain curves of MXene/ink (mass ratio of 1:25 to 1:5) in examples 1 and 3 for tensile property testing of the composite material, and it can be seen that as the ratio of MXene increases, the strain sensing coefficient of the sensor decreases.
Fig. 8 shows the curves of the MXene/ink (mass ratio of 1:75 and 1:5) detection of the composite material under the micro-strain (0% to 0.06%), which can be shown that the mechanical properties of the composite material can be monitored under the micro-strain condition, the sensitivity of the sensor with the mass ratio of 1:5 is reduced significantly (4,4.5,4.67), and the sensitivity of the sensor with the mass ratio of 1:75 can reach (92.5,92.75,92.3) under the micro-strain condition.
Fig. 9 shows the response of the MXene/ink temperature sensor to temperature in example 4, and it can be seen that the resistance change rate of the sensor is consistent with the response of the change of temperature, the temperature rises to 120 ℃, the resistance change can reach 0.16, and the temperature returns to room temperature, the sensor can return to the initial value, and multiple uses can be realized.
Fig. 10 shows a data graph of monitoring and measuring the pressure relief of the metal pressure container by the MXene/ink temperature sensor in example 4, and the used sensor can still keep a good service state after 3000 times of fatigue tests.
Fig. 11 shows a curve of detecting tensile properties of the composite material by the MXene/ink sensor after the polymeric chelating agent and the high-valence metal ions are added and dispersed in the comparative example 7, compared with the MXene/ink sensor which is prepared in the same manner without adding the high-valence metal ions in the example 1, the sensor with the high-valence metal ions added has a lower sensing coefficient, and after the strain reaches a certain value, the resistance change rate of the sensor changes suddenly, so that a sensing image is very unstable.
Figure 12 shows the dispersion of MXene in DMSO at different stages in example 8, as shown in figures a-f, where a is the treated image after stirring only, and a large number of undispersed lumps of MXene were observed with significant aggregation. b is an image subjected to one-time ultrasonic dispersion, massive MXene is decomposed, but the decomposed MXene cannot be completely dispersed in DMSO, further dispersion is needed, c is an image subjected to first centrifugal impurity removal treatment, it can be seen that the centrifugation step is indispensable in layer-by-layer dispersion, a small amount of undispersed MXene can be removed through centrifugation, d is an image subjected to five-time dispersion processes, multiple dispersion processes can be observed, the MXene can be completely dispersed, however, the MXene content is very low, loss occurs after each dispersion, and the appropriate dispersion times are selected according to the type of a dispersion solution. And e is the image processed by the three-time dispersion process, and is in the optimal dispersion state, so the optimal dispersion times in DMSO are f, i.e., the image processed by the three-time stirring and ultrasonic dispersion and not subjected to impurity removal treatment, MXene can be mostly dispersed after the three-time dispersion process, and the comparison with the image e shows that the impurity removal treatment is required after each dispersion.
Although specific embodiments of the present invention have been described above, it will be appreciated by those skilled in the art that these are merely examples and that many variations or modifications may be made to the embodiments without departing from the principles and spirit of the invention, the scope of which is defined in the appended claims.
Claims (10)
1. The MXene/ink high-sensitivity sensor is characterized in that a sensing active component of the MXene/ink high-sensitivity sensor without high-valence metal ions is a composite structure of an MXene material and ink, the size range of the MXene material is 200-500 nm, the MXene material is completely dispersed in the ink, and the composite structure does not contain the high-valence metal ions except the MXene material.
2. The MXene/ink high sensitivity sensor free of high valent metal ions of claim 1, wherein the active component of the MXene/ink high sensitivity sensor free of high valent metal ions is coated on a test substrate or surface of a substrate.
3. The MXene/ink high sensitivity sensor without high valence metal ions according to claim 1 or 2, wherein the ink is one of solvent-based ink, water-soluble ink or UV ink, and the mass ratio of the MXene material to the ink is 1: (1-100).
4. The MXene/ink high sensitivity sensor without high valence metal ions of claim 2, wherein the test substrate is one of a composite, metal, ceramic or plastic.
5. The MXene/ink high sensitivity sensor without high valence metal ions of claim 1 or 2, wherein the MXene/ink high sensitivity sensor without high valence metal ions is a piezoresistive sensor, a strain sensor or a temperature sensor, and the active member size is 10mm x (10-30) mm.
6. The MXene/ink high sensitivity sensor without high valent metal ions of claim 1 or 2, wherein the MXene/ink high sensitivity sensor without high valent metal ions is capable of achieving control of sensitivity by varying the mass ratio of the MXene to the ink.
7. The method for preparing MXene/ink high sensitivity sensor without high valence metal ions as claimed in claim 1, comprising the steps of:
step (1): stirring MXene materials in a dispersion solvent, performing ultrasonic dispersion treatment, centrifuging at the rotating speed of 3000r/min, and removing impurities in the solution; repeating the stirring, ultrasonic dispersion treatment, centrifuging and impurity removal dispersion processes for 3-5 times, gradually reducing the ultrasonic dispersion power within the range of 100-50W in each time to prepare MXene dispersion liquid, and adding the dispersion liquid into the ink in proportion;
step (2): uniformly mixing the MXene/ink mixture obtained in the step (1) through a dispersion process, and removing a dispersion solvent to obtain an MXene/ink composite material;
and (3): coating the prepared MXene/printing ink composite material on a test base material or the surface of a substrate, and curing;
and (4): and respectively connecting one ends of two wires to two ends of the surface of the MXene/printing ink composite material, coating conductive silver paste to bond the wires and the MXene/printing ink composite material, drying the conductive silver paste, and connecting the other ends of the two wires to the signal conversion element.
8. The method for preparing MXene/ink high sensitivity sensor without high valence metal ions according to claim 7, wherein the dispersion solvent in step (1) is one of toluene, water, acetone, and dimethyl sulfoxide.
9. The method for preparing MXene/ink high sensitivity sensor without high valence metal ions according to claim 7, wherein the dispersion process in step (2) is one of mechanical grinding dispersion, ultrasonic dispersion or adding dispersant; the method for removing the dispersion solvent in the step (2) is one of a vacuum drying method, a freeze-drying method or a molecular sieve method.
10. The method for preparing the MXene/ink high sensitivity sensor without high valence metal ions according to claim 7, wherein the method for coating the MXene/ink composite material in the step (3) is one of screen printing, thermal transfer printing or printer spray forming.
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