CN113087972A - MXene/silver nanowire/nanocellulose composite film and preparation method thereof - Google Patents
MXene/silver nanowire/nanocellulose composite film and preparation method thereof Download PDFInfo
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Abstract
The invention discloses an MXene/silver nanowire/nanocellulose composite film and a preparation method thereof. The method mainly comprises the following steps: (1) etching MAX to prepare a single-layer MXene colloidal solution; (2) preparing a silver nanowire colloidal solution; (3) preparing a carboxylated nano cellulose colloidal solution by a TEMPO oxidation method; (4) mixing the three colloidal solutions according to a certain mass ratio, stirring and carrying out ice bath ultrasound to obtain a uniform mixed solution; (5) and carrying out vacuum filtration and hot-pressing drying on the mixed solution to obtain the MXene/silver nanowire/nano-cellulose composite film. The invention provides a preparation method of an MXene/silver nanowire/nanocellulose composite film, and the prepared composite film has good flexibility, electrochemical performance, electromagnetic shielding performance and antibacterial performance, and has wide application prospects in the fields of aerospace, weaponry, flexible wearable equipment and the like.
Description
Technical Field
The invention relates to the technical field of energy materials, in particular to an MXene/silver nanowire/nanocellulose composite film and a preparation method thereof.
Background
In recent years, flexible wearable electronic devices have a wide prospect in the application fields of portable mobile electronic equipment, novel energy storage equipment, human motion detection and the like, and are widely concerned by researchers. At present, a great deal of research is devoted to developing materials with different structures and functions, especially the application in the fields of sensors, supercapacitors, electromagnetic shielding and the like. Therefore, the design principle of the flexible wearable material is optimized, and the sensor with good linearity, high sensitivity and wide working range is developed; developing a multifunctional wearable device integrating good mechanical performance, electrochemical performance, mould resistance, antibiosis and good electromagnetic shielding performance; development of fibers, fabrics and the like with wearable comfort and air permeability is a future development direction of composite materials in the field of flexible wearable devices.
Two-dimensional materials, such as graphene, black phosphorus, MXene, transition metal sulfides, etc., have been widely studied due to their unique physicochemical properties, high specific surface area, and excellent electronic and mechanical properties. Particularly, the two-dimensional flaky nano material MXene emerging in recent years is mainly two-dimensional transition metal carbide, nitride or carbonitride, and most researches currently comprise Ti3C2、Ti2C、V2C、Nb4C3And the like, have excellent electrical conductivity, thermal conductivity, photothermal properties, hydrophilic properties, antibacterial properties, mechanical properties, and the like, and hold a place in the fields of energy, environment, biomedical use, and the like. However, MXene is due to the strong interpenetration between adjacent nanoplateletsVan der waals interactions, during suction filtration and drying, tend to cause nanosheet stacking and self-aggregation, resulting in a dramatic decrease in available surface area and an increase in charge transport resistance.
Silver nanowires, which are the most representative metal wires with nanoscale one-dimensional structures, are hot spots in research in the fields of microelectronic devices, microelectrodes, biosensors, thin-film solar cells, catalysts, and the like in recent years. The special one-dimensional structure can provide a pore channel for electron transmission, so that the conductive material has excellent conductivity (the conductivity is as high as 6.3 multiplied by 10)7S/m) and low surface resistance. Meanwhile, due to the size effect of the nanometer level, the conductive network has excellent light transmission and bending resistance, and the possibility of realizing a flexible and bendable electronic device is provided. In addition, silver nanowires also have biocompatibility and antibacterial properties and are widely used in the fields of sensors and microelectrodes.
The cellulose nanofiber serving as a natural one-dimensional nanomaterial has the advantages of wide natural biomass material source, environmental friendliness and the like, and has excellent physicochemical properties of high length-diameter ratio, good flexibility, rich surface functional groups and the like. However, CNFs do not have electrical conductivity, and impart excellent mechanical properties to flexible materials, and also pose a problem of low electrical conductivity.
In order to solve the problems among the raw materials and improve the performance of the MXene membrane electrode material, the invention introduces silver nanowires to increase the specific surface area and the interlayer conductivity and introduces nanocellulose intercalation to avoid the blockage and the reduction of the specific surface area after the MXene membrane is formed. In addition, the addition of the silver nanowires and the nanocellulose plays a role in enhancing the flexibility and the mechanical performance of the composite film, so that the composite film has multiple excellent performances.
Disclosure of Invention
The invention provides an MXene/silver nanowire/nanocellulose composite film and a preparation method thereof, and aims to solve the problem that the performance cannot be further improved due to MXene nanosheet layer stacking. In addition, the development of the field is limited by the problems that the electrochemical performance and the mechanical performance of the current film material cannot be combined, the function is single, the preparation is complex and the like. The composite film prepared by the invention has good flexibility, electrochemical performance, electromagnetic shielding performance and antibacterial performance, and has wide application prospects in the fields of aerospace, weaponry, flexible wearable equipment and the like.
The technical solution of the invention is as follows: an MXene/silver nanowire/nano-cellulose composite film and a preparation method thereof comprise the following process steps:
(1) preparing 1-5 mg/mL monolayer MXene colloidal solution;
(2) preparing 1-5 mg/mL silver nanowire colloidal solution;
(3) preparing 0.1-1 wt% of carboxylated nano cellulose fiber colloidal solution;
(4) mixing the three colloidal solutions according to a certain mass ratio, adding deoxygenated deionized water for dilution, diluting to a constant volume of 30-40 mL, stirring for 3-6 h, and carrying out ice bath ultrasound for 15-30 min to obtain a uniform mixed solution, wherein the mass fraction of an active substance MXene/silver nanowire is 60-90%, and the mass ratio of MXene to silver nanowire is 10: 0.5-1: 1;
(5) carrying out vacuum auxiliary suction filtration on the mixed solution obtained in the step (4) to obtain a colloidal MXene/silver nanowire/nano-cellulose composite sheet;
(6) and (3) drying the sheet obtained in the step (5) at the temperature of 60-80 ℃ for 1-2 h by means of vacuum hot pressing to obtain the MXene/silver nanowire/nanocellulose composite film.
Further, in the step (1), the single-layer MXene colloidal solution is prepared by the following method:
(1) slowly dissolving 1.5-1.8 g of lithium fluoride in 15-25 mL of 9M hydrochloric acid, and stirring for 5-10 min to obtain a clear corrosive solution;
(2) slowly adding 0.8-1.2 g of Ti3AlC2 into the corrosive liquid, stirring for 20-28 h at 45 ℃, washing and centrifuging for 6-8 times by using deionized water, wherein the centrifugal rotating speed is 3000-4000 rpm, centrifuging for 5min each time, and the pH value of supernatant is more than 6;
(3) collecting the precipitate, dissolving the precipitate in 80-120 mL of deionized water, and performing ultrasonic treatment for 3-4 h under the argon atmosphere;
(4) centrifuging the solution subjected to ultrasonic treatment for 1-1.5 h at the centrifugal rotating speed of 3000-4000 rpm, and collecting supernatant to obtain a single-layer MXene colloidal solution;
(5) taking a certain amount of the solution obtained in the step (4), performing vacuum-assisted suction filtration through a 0.22-micron microporous filter membrane, drying under the protection of nitrogen, and weighing the mass difference between the front and the rear of the filter membrane to obtain the concentration of the MXene monolayer colloidal solution;
(6) and adding deoxygenated deionized water to prepare a 1-5 mg/mL monolayer MXene colloidal solution, and storing for later use under the protection of nitrogen.
Further, in the step (2), the silver nanowire colloidal solution is prepared by the following method:
(1) weighing 13-18 g of silver nitrate and 13-18 g of polyvinylpyrrolidone (PVP) in 250-350 mL of ethylene glycol, and carrying out ultrasonic treatment for 15-30 min until the silver nitrate and the PVP are completely dissolved to obtain a colorless transparent solution;
(2) measuring 20mL of 0.14M copper chloride glycol solution, measuring 5-20 mL of 0.14M sodium bromide glycol solution, adding the solution, and stirring for 20-30 min to obtain a milky mixed solution;
(3) weighing 4-7 g of stainless steel fibers in the mixed solution, and standing at a constant temperature of 150-170 ℃ for 5-7 h to obtain a gray product accompanied with silver wires and obtain a silver nanowire stock solution;
(4) centrifuging the stock solution, alternately washing the product with ethanol and deionized water for 3-5 times, adding deionized water for dispersion to obtain 1-5 mg/mL silver nanowire colloidal solution, and refrigerating the silver nanowire colloidal solution in a refrigerator at 4-6 ℃ for later use.
Further, in the step (3), the carboxylated nano cellulose fiber colloidal solution is prepared by the following method:
(1) dispersing 18-22 g of absolutely dry softwood pulp in deionized water through mechanical stirring to form 1 wt% of uniform slurry;
(2) weighing 0.3-0.35 g of 2,2,6, 6-tetramethylpiperidine-nitrogen-oxide (TEMPO) and 2.3-2.35 g of sodium bromide, dissolving in the slurry, and performing ultrasonic dispersion for 10-20 min;
(3) slowly adding 280-290 g of sodium hypochlorite (6.3 percent of available chlorine content), and stirring at 30 ℃;
(4) dropwise adding 0.5M sodium hydroxide to maintain the pH value within the range of 9.7-10.2, reacting for 4-6 h, dropwise adding 200-220 mL of ethanol, and dropwise adding a hydrochloric acid solution to adjust the pH value to be about 7;
(5) washing the oxidized wood pulp fiber by using deionized water, dispersing the washed product in water, centrifuging for 30-40 min at 8000-10000 rpm, and collecting supernatant;
(6) homogenizing the supernatant under high pressure to prepare 0.1-1 wt% TEMPO oxidized nano cellulose fiber colloidal solution, and refrigerating in a refrigerator at 4-6 ℃ for later use.
Further, in the step (4), the stirring is mechanical stirring or magnetic stirring, and the rotating speed is 500-2000 rpm.
Further, in the step (5), the extraction filter membrane is an aqueous cellulose filter membrane, and the pore diameter is 0.22 μm or 0.45 μm.
The invention has the beneficial effects that the nano cellulose fiber is used as a high polymer reinforcement and also used as an intercalation function, and MXene lamellar stacking is avoided. A three-dimensional conductive network structure is constructed by taking the one-dimensional silver nanowire and the two-dimensional MXene nanosheet as conductive materials, and meanwhile, the carbonyl on the surface of the silver nanowire and the hydroxyl on the surface of the MXene form a hydrogen bond effect, so that the excellent electrochemical performance and the electromagnetic shielding performance of the film can be guaranteed. The nano-cellulose in the raw materials is a natural polymer material, has wide sources, is degradable, has low price, meets the requirement of green chemistry, can expand the application range of biomass materials, and realizes the high-value utilization of inferior wood of fast-growing woods of artificial forests and forest wood resources. The preparation process is safe and environment-friendly, the process flow is simple, and the production period is short. The prepared MXene/silver nanowire/nanocellulose composite film has excellent performance, has the multifunctional characteristics of good flexibility, electrochemical performance, electromagnetic shielding performance, antibacterial performance and the like, has wide application prospect in the fields of aerospace, weaponry, flexible wearable equipment and the like, and has large-scale commercial production value.
Drawings
Fig. 1 is a flow chart of an MXene/silver nanowire/nanocellulose composite film and a preparation method thereof provided by the invention;
fig. 2 is an SEM image of the MXene/silver nanowire/nanocellulose composite film in example 1 of the present invention;
fig. 3 is an EDS diagram of an MXene/silver nanowire/nanocellulose composite film in example 1 of the present invention;
fig. 4 is a conductivity test chart of the MXene/silver nanowire/nanocellulose composite film in example 2 of the present invention;
FIG. 5 shows that the thickness of the MXene/silver nanowire/nanocellulose composite film in example 1 of the present invention is 0.4mA/cm-2、0.5mA/cm-2、0.6mA/cm-2、1mA/cm-2、2mA/cm-2、5mA/cm-2Constant current charge and discharge test chart under current density;
FIG. 6 is a cyclic voltammetry test chart of the MXene/silver nanowire/nanocellulose composite film under a sweep rate of 50mV/s in example 1 of the present invention;
FIG. 7 shows that the thickness of the MXene/silver nanowire/nanocellulose composite film in example 2 of the present invention is 0.4mA/cm-2、0.5mA/cm-2、1mA/cm-2、2mA/cm-2、5mA/cm-2Constant current charge and discharge test chart under current density;
FIG. 8 is a cyclic voltammetry test chart of the MXene/silver nanowire/nanocellulose composite film in the sweep rate of 50mV/s in example 2 of the present invention.
Detailed Description
The present invention will be specifically described below with reference to specific examples, but the present invention is not limited thereto.
Example 1
An MXene/silver nanowire/nano-cellulose composite film and a preparation method thereof comprise the following process steps:
(1) slowly dissolving 1.6g of lithium fluoride in 20mL of 9M hydrochloric acid, and stirring for 10min to obtain a clear corrosive solution; slowly adding 1g of Ti into the corrosive liquid3AlC2Stirring for 24h at 45 ℃, washing and centrifuging for 7 times by using deionized water, wherein the centrifugal rotating speed is 3500rpm, and centrifuging for 5min each time until the pH value of supernatant is more than 6; collecting the precipitate, dissolving the precipitate in 100mL of deionized water, and performing ultrasonic treatment for 3h under the argon atmosphere; centrifuging the solution after ultrasonic treatment for 1.5h at the centrifugal rotation speed of 3500rpm, and collecting supernatant to obtain a monolayer MXene colloidal solution; taking a certain amount of the obtained solution, vacuum-assisted filtering with 0.22 μm microporous membrane, drying under nitrogen protection, weighing, and filteringThe quality of the film is poor before and after the film is formed, and the concentration of MXene single-layer colloidal solution is obtained; adding deoxidized deionized water to prepare a monolayer MXene colloidal solution of 3mg/mL, and storing for later use under the protection of nitrogen.
(2) Weighing 15.3g of silver nitrate and 15g of polyvinylpyrrolidone (PVP) in 300mL of ethylene glycol, and carrying out ultrasonic treatment for 15min until the silver nitrate and the polyvinylpyrrolidone are completely dissolved to obtain a colorless transparent solution; measuring 20mL of 0.14M copper chloride glycol solution, simultaneously measuring 15mL of 0.14M sodium bromide glycol solution, adding the solution, and stirring for 20min to obtain milky mixed solution; weighing 5g of stainless steel fibers in the mixed solution, standing for 6h at constant temperature of 160 ℃ to obtain a gray product accompanied with silver wires, and obtaining a silver nanowire stock solution; centrifuging the stock solution, alternately washing the product with ethanol and deionized water for 4 times, adding deionized water for dispersion to obtain 1mg/mL silver nanowire colloidal solution, and refrigerating in a refrigerator at 6 ℃ for later use.
(3) Dispersing 20g of absolutely dry softwood pulp in deionized water by mechanical stirring to form 1 wt% of uniform slurry; weighing 0.33g of 2,2,6, 6-tetramethylpiperidine-nitrogen-oxide (TEMPO) and 2.33g of sodium bromide, dissolving in the slurry, and ultrasonically dispersing for 15 min; 285g of sodium hypochlorite (6.3% available chlorine content) was added slowly and stirred at 30 ℃; dropwise adding 0.5M sodium hydroxide to maintain the pH value within the range of 9.7-10.2, after reacting for 5 hours, dropwise adding 200mL of ethanol, and dropwise adding a hydrochloric acid solution to adjust the pH value to be about 7; washing the oxidized wood pulp fiber with deionized water, dispersing the washed product in water, centrifuging at 10000rpm for 30min, and collecting supernatant; homogenizing the supernatant under high pressure to obtain 0.5 wt% TEMPO oxidized nanometer cellulose fiber colloidal solution, and refrigerating at 6 deg.C in refrigerator.
(4) Taking 5mL of 3mg/mL MXene colloidal solution, 5mL of 1mg/mL silver nanowire colloidal solution and 1g of 0.5 wt% nano-cellulose colloidal solution, adding the three colloidal solutions into a glass split charging bottle, adding deoxygenated deionized water to a constant volume of 30mL, magnetically stirring at a rotation speed of 1000rpm for 5h, and performing ice bath ultrasound for 20min to obtain a uniform mixed solution.
(5) And (4) performing vacuum auxiliary suction filtration on the mixed solution obtained in the step (4) through a water-based cellulose filter membrane with the aperture of 0.22 mu m to obtain the colloidal MXene/silver nanowire/nano-cellulose composite sheet.
(6) And (4) carrying out vacuum hot-pressing drying on the thin sheet obtained in the step (5) at the temperature of 70 ℃ for 1.5h to obtain the MXene/silver nanowire/nano-cellulose composite film.
Example 2
An MXene/silver nanowire/nano-cellulose composite film and a preparation method thereof comprise the following process steps:
(1) slowly dissolving 1.8g of lithium fluoride in 25mL of 9M hydrochloric acid, and stirring for 10min to obtain a clear corrosive solution; slowly adding 1.2g of Ti into the corrosive liquid3AlC2Stirring for 28h at 45 ℃, washing and centrifuging for 8 times by using deionized water, wherein the centrifugal rotating speed is 3500rpm, and centrifuging for 5min each time until the pH value of supernatant is more than 6; collecting the precipitate, dissolving in 100mL deionized water, and performing ultrasonic treatment for 3.5h under the argon atmosphere; centrifuging the solution after ultrasonic treatment for 1.5h at the centrifugal rotation speed of 3500rpm, and collecting supernatant to obtain a monolayer MXene colloidal solution; taking a certain amount of the obtained solution, carrying out vacuum-assisted suction filtration through a 0.22-micron microporous filter membrane, drying under the protection of nitrogen, and weighing the mass difference between the front and the rear of the filter membrane to obtain the concentration of the MXene monolayer colloidal solution; adding deoxygenated deionized water to prepare a 1mg/mL monolayer MXene colloidal solution, and storing for later use under the protection of nitrogen.
(2) Weighing 15g of silver nitrate and 16g of polyvinylpyrrolidone (PVP) in 350mL of ethylene glycol, and carrying out ultrasonic treatment for 15min until the silver nitrate and the PVP are completely dissolved to obtain a colorless transparent solution; measuring 20mL of 0.14M copper chloride glycol solution, simultaneously measuring 10mL of 0.14M sodium bromide glycol solution, adding the solution, and stirring for 25min to obtain milky mixed solution; weighing 6g of stainless steel fibers in the mixed solution, and standing at the constant temperature of 170 ℃ for 5h to obtain a gray product accompanied with silver wires, thereby obtaining a silver nanowire stock solution; centrifuging the stock solution, alternately washing the product with ethanol and deionized water for 5 times, adding deionized water for dispersion to obtain 1mg/mL silver nanowire colloidal solution, and refrigerating in a refrigerator at 6 ℃ for later use.
(3) Dispersing 18g of absolutely dry softwood pulp in deionized water by mechanical agitation to form a 1 wt% homogeneous slurry; weighing 0.3g of 2,2,6, 6-tetramethylpiperidine-nitrogen-oxide (TEMPO) and 2.3g of sodium bromide, dissolving in the slurry, and performing ultrasonic dispersion for 10 min; slowly adding 280g of sodium hypochlorite (6.3% available chlorine content), and stirring at 30 ℃; dropwise adding 0.5M sodium hydroxide to maintain the pH value within the range of 9.7-10.2, reacting for 4.5 hours, dropwise adding 200mL of ethanol, and dropwise adding a hydrochloric acid solution to adjust the pH value to be about 7; washing the oxidized wood pulp fiber by deionized water, dispersing the washed product in water, centrifuging at 9000rpm for 35min, and collecting supernatant; homogenizing the supernatant under high pressure to obtain 0.1 wt% TEMPO oxidized nanometer cellulose fiber colloidal solution, and refrigerating at 6 deg.C in refrigerator.
(4) Taking 11mL of 1mg/mL MXene colloidal solution, 11mL of 1mg/mL silver nanowire colloidal solution and 3g of 0.1 wt% nano-cellulose colloidal solution, adding the three colloidal solutions into a glass split charging bottle, adding deoxygenated deionized water to a constant volume of 30mL, magnetically stirring at a rotation speed of 1500rpm for 4h, and performing ice bath ultrasound for 20min to obtain a uniform mixed solution.
(5) And (4) performing vacuum auxiliary suction filtration on the mixed solution obtained in the step (4) through a water-based cellulose filter membrane with the aperture of 0.22 mu m to obtain the colloidal MXene/silver nanowire/nano-cellulose composite sheet.
(6) And (4) carrying out vacuum hot-pressing drying on the thin sheet obtained in the step (5) at the temperature of 60 ℃ for 2h to obtain the MXene/silver nanowire/nano-cellulose composite film.
Example 3
An MXene/silver nanowire/nano-cellulose composite film and a preparation method thereof comprise the following process steps:
(1) slowly dissolving 1.5g of lithium fluoride in 15mL of 9M hydrochloric acid, and stirring for 10min to obtain a clear corrosive solution; slowly adding 0.8g of Ti into the corrosive liquid3AlC2Stirring for 20h at 45 ℃, washing and centrifuging for 6 times by using deionized water, wherein the centrifugal rotating speed is 4000rpm, and centrifuging for 5min each time until the pH value of supernatant is more than 6; collecting the precipitate, dissolving the precipitate in 80mL of deionized water, and performing ultrasonic treatment for 3h under the argon atmosphere; centrifuging the solution subjected to ultrasonic treatment for 1h at the rotation speed of 4000rpm, and collecting supernatant to obtain a monolayer MXene colloidal solution; taking a certain amount of the obtained solution, carrying out vacuum-assisted suction filtration through a 0.22-micron microporous filter membrane, drying under the protection of nitrogen, and weighing the mass difference between the front and the rear of the filter membrane to obtain the concentration of the MXene monolayer colloidal solution; adding deoxygenated deionized water to prepare 1mg/mL monolayer MXene colloidal solution, and storing under the protection of nitrogenThe application is as follows.
(2) Weighing 13g of silver nitrate and 13g of polyvinylpyrrolidone (PVP) in 250mL of ethylene glycol, and carrying out ultrasonic treatment for 15min until the silver nitrate and the polyvinylpyrrolidone are completely dissolved to obtain a colorless transparent solution; measuring 20mL of 0.14M copper chloride glycol solution, simultaneously measuring 20mL of 0.14M sodium bromide glycol solution, adding the solution, and stirring for 20min to obtain milky mixed solution; weighing 5g of stainless steel fibers in the mixed solution, standing for 6h at constant temperature of 160 ℃ to obtain a gray product accompanied with silver wires, and obtaining a silver nanowire stock solution; centrifuging the stock solution, alternately washing the product with ethanol and deionized water for 4 times, adding deionized water for dispersion to obtain 1mg/mL silver nanowire colloidal solution, and refrigerating in a refrigerator at 6 ℃ for later use.
(3) Dispersing 22g of absolutely dry softwood pulp in deionized water by mechanical agitation to form a 1 wt% homogeneous slurry; weighing 0.35g of 2,2,6, 6-tetramethylpiperidine-nitrogen-oxide (TEMPO) and 2.35g of sodium bromide, dissolving in the slurry, and performing ultrasonic dispersion for 20 min; 290g of sodium hypochlorite (6.3% active chlorine content) was slowly added and stirred at 30 ℃; dropwise adding 0.5M sodium hydroxide to maintain the pH value within the range of 9.7-10.2, reacting for 6 hours, dropwise adding 220mL ethanol, and dropwise adding a hydrochloric acid solution to adjust the pH value to be about 7; washing the oxidized wood pulp fiber with deionized water, dispersing the washed product in water, centrifuging at 10000rpm for 30min, and collecting supernatant; homogenizing the supernatant under high pressure to obtain 1 wt% TEMPO oxidized nanometer cellulose fiber colloid solution, and refrigerating at 6 deg.C in refrigerator.
(4) Taking 14mL of 1mg/mL MXene colloidal solution, 1mL of 1mg/mL silver nanowire colloidal solution and 1g of 1 wt% nano-cellulose colloidal solution, adding the three colloidal solutions into a glass subpackage bottle, adding deoxygenated deionized water to a constant volume of 40mL, magnetically stirring at a rotating speed of 2000rpm for 5h, and performing ice bath ultrasound for 15min to obtain a uniform mixed solution.
(5) And (4) performing vacuum auxiliary suction filtration on the mixed solution obtained in the step (4) through a water-based cellulose filter membrane with the aperture of 0.45 mu m to obtain the colloidal MXene/silver nanowire/nano-cellulose composite sheet.
(6) And (4) carrying out vacuum hot-pressing drying on the thin sheet obtained in the step (5) at the temperature of 80 ℃ for 1h to obtain the MXene/silver nanowire/nano-cellulose composite film.
The above-mentioned embodiments are merely illustrative of the preferred embodiments of the present invention, and should not be construed as limiting the scope of the invention, and any other changes, modifications, simplifications, substitutions, combinations, and equivalents which do not depart from the spirit and principle of the present invention should be construed as being included in the scope of the claims of the present invention.
Claims (7)
1. An MXene/silver nanowire/nano-cellulose composite film and a preparation method thereof are characterized by comprising the following steps:
(1) preparing 1-5 mg/mL monolayer MXene colloidal solution;
(2) preparing 1-5 mg/mL silver nanowire colloidal solution;
(3) preparing 0.1-1 wt% of carboxylated nano cellulose fiber colloidal solution;
(4) mixing the three colloidal solutions according to a certain mass ratio, adding deoxygenated deionized water for dilution, diluting to a constant volume of 30-40 mL, stirring for 3-6 h, and carrying out ice bath ultrasound for 15-30 min to obtain a uniform mixed solution, wherein the mass fraction of an active substance MXene/silver nanowire is 60-90%, and the mass ratio of MXene to silver nanowire is 10: 0.5-1: 1;
(5) carrying out vacuum auxiliary suction filtration on the mixed solution obtained in the step (4) to obtain a colloidal MXene/silver nanowire/nano-cellulose composite sheet;
(6) and (3) drying the sheet obtained in the step (5) at the temperature of 60-80 ℃ for 1-2 h by means of vacuum hot pressing to obtain the MXene/silver nanowire/nanocellulose composite film.
2. The preparation method according to claim 1, wherein in the step (1), the single-layer MXene colloidal solution is prepared by:
(1) slowly dissolving 1.5-1.8 g of lithium fluoride in 15-25 mL of 9M hydrochloric acid, and stirring for 5-10 min to obtain a clear corrosive solution;
(2) slowly adding 0.8-1.2 g of Ti into the corrosive liquid3AlC2Stirring for 20-28 h at 45 ℃, washing and centrifuging for 6-8 times by using deionized waterCentrifuging at 3000-4000 rpm for 5min until the pH value of the supernatant is greater than 6;
(3) collecting the precipitate, dissolving the precipitate in 80-120 mL of deionized water, and performing ultrasonic treatment for 3-4 h under the argon atmosphere;
(4) centrifuging the solution subjected to ultrasonic treatment for 1-1.5 h at the centrifugal rotating speed of 3000-4000 rpm, and collecting supernatant to obtain a single-layer MXene colloidal solution;
(5) taking a certain amount of the solution obtained in the step (4), performing vacuum-assisted suction filtration through a 0.22-micron microporous filter membrane, drying under the protection of nitrogen, and weighing the mass difference between the front and the rear of the filter membrane to obtain the concentration of the MXene monolayer colloidal solution;
(6) and adding deoxygenated deionized water to prepare a 1-5 mg/mL monolayer MXene colloidal solution, and storing for later use under the protection of nitrogen.
3. The method according to claim 1, wherein in the step (2), the silver nanowire colloidal solution is prepared by:
(1) weighing 13-18 g of silver nitrate and 13-18 g of polyvinylpyrrolidone (PVP) in 250-350 mL of ethylene glycol, and carrying out ultrasonic treatment for 15-30 min until the silver nitrate and the PVP are completely dissolved to obtain a colorless transparent solution;
(2) measuring 20mL of 0.14M copper chloride glycol solution, measuring 5-20 mL of 0.14M sodium bromide glycol solution, adding the solution, and stirring for 20-30 min to obtain a milky mixed solution;
(3) weighing 4-7 g of stainless steel fibers in the mixed solution, and standing at a constant temperature of 150-170 ℃ for 5-7 h to obtain a gray product accompanied with silver wires and obtain a silver nanowire stock solution;
(4) centrifuging the stock solution, alternately washing the product with ethanol and deionized water for 3-5 times, adding deionized water for dispersion to obtain 1-5 mg/mL silver nanowire colloidal solution, and refrigerating the silver nanowire colloidal solution in a refrigerator at 4-6 ℃ for later use.
4. The preparation method according to claim 1, wherein in the step (3), the carboxylated nano cellulose fiber colloidal solution is prepared by the following method:
(1) dispersing 18-22 g of absolutely dry softwood pulp in deionized water through mechanical stirring to form 1 wt% of uniform slurry;
(2) weighing 0.3-0.35 g of 2,2,6, 6-tetramethylpiperidine-nitrogen-oxide (TEMPO) and 2.3-2.35 g of sodium bromide, dissolving in the slurry, and performing ultrasonic dispersion for 10-20 min;
(3) slowly adding 280-290 g of sodium hypochlorite (6.3 percent of available chlorine content), and stirring at 30 ℃;
(4) dropwise adding 0.5M sodium hydroxide to maintain the pH value within the range of 9.7-10.2, reacting for 4-6 h, dropwise adding 200-220 mL of ethanol, and dropwise adding a hydrochloric acid solution to adjust the pH value to be about 7;
(5) washing the oxidized wood pulp fiber by using deionized water, dispersing the washed product in water, centrifuging for 30-40 min at 8000-10000 rpm, and collecting supernatant;
(6) homogenizing the supernatant under high pressure to prepare 0.1-1 wt% TEMPO oxidized nano cellulose fiber colloidal solution, and refrigerating in a refrigerator at 4-6 ℃ for later use.
5. The preparation method according to claim 1, wherein in the step (4), the stirring is mechanical stirring or magnetic stirring, and the rotating speed is 500-2000 rpm.
6. The production method according to claim 1, wherein in the step (5), the suction filtration membrane is an aqueous cellulose filtration membrane having a pore size of 0.22 μm or 0.45 μm.
7. The application of the MXene/silver nanowire/nanocellulose composite film prepared by the preparation method according to claim 1 is characterized in that: the prepared composite film has good flexibility, electrochemical performance, electromagnetic shielding performance and antibacterial performance, and has wide application prospects in the fields of aerospace, weaponry, flexible wearable equipment and the like.
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