CN114605667A - Preparation method of tannic acid functionalized carbon nanotube/graphene composite hydrogel - Google Patents
Preparation method of tannic acid functionalized carbon nanotube/graphene composite hydrogel Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/02—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques
- C08J3/03—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques in aqueous media
- C08J3/075—Macromolecular gels
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2329/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal, or ketal radical; Hydrolysed polymers of esters of unsaturated alcohols with saturated carboxylic acids; Derivatives of such polymer
- C08J2329/02—Homopolymers or copolymers of unsaturated alcohols
- C08J2329/04—Polyvinyl alcohol; Partially hydrolysed homopolymers or copolymers of esters of unsaturated alcohols with saturated carboxylic acids
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/001—Conductive additives
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/02—Elements
- C08K3/04—Carbon
- C08K3/041—Carbon nanotubes
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/02—Elements
- C08K3/04—Carbon
- C08K3/042—Graphene or derivatives, e.g. graphene oxides
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K9/00—Use of pretreated ingredients
- C08K9/04—Ingredients treated with organic substances
Abstract
The invention discloses a preparation method of tannic acid functionalized carbon nanotube/graphene composite hydrogel, which comprises the following steps: adding a carbon nano tube, tannic acid and graphene into a solvent for dissolving, performing ultrasonic treatment, performing heating reaction in an oil bath, performing suction filtration, washing, and performing cold drying to obtain a tannic acid functionalized carbon nano tube/graphene; then adding polyvinyl alcohol into deionized water, stirring, and heating in an oil bath to obtain a solution; and then adding the tannic acid functionalized carbon nano tube/graphene into deionized water, stirring, mixing with the solution, carrying out oil bath heating and stirring to obtain a mixed solution, pouring the mixed solution into a polytetrafluoroethylene mold, and carrying out freeze-thaw cycling. The tannin functionalized carbon nanotube/graphene composite hydrogel enhances the dispersibility of the conductive filler in the gel matrix, improves the conductivity and mechanical properties of the hydrogel, and can be used for pressure/strain sensors.
Description
Technical Field
The invention belongs to the technical field of nano composite materials, and particularly relates to a preparation method of tannic acid functionalized carbon nanotube/graphene composite hydrogel.
Background
Wearable sensors typically have elastomeric and polymeric films as matrix materials, but they suffer from low stretchability, flexibility and poor durability, and complex manufacturing processes, limiting their further application as wearable devices. Therefore, the development of the flexible sensor with low cost, simple process and excellent comprehensive performance has great significance for the further development of wearable electronic equipment. The hydrogel is a soft material with a structure similar to that of natural living tissues, has good flexibility and biocompatibility, and has remarkable flexibility in designing a network structure, mechanical properties and functional characteristics, so that the hydrogel becomes one of ideal flexible matrix materials of next-generation flexible electronic devices.
The carbon-based materials such as the carbon nano tube and the graphene have excellent conductivity and higher strength, and the carbon materials and the polymer hydrogel are compounded with each other, so that the mechanical property of the hydrogel can be improved, and the hydrogel can be endowed with excellent conductivity. However, since the carbon nanotubes and graphene are easily agglomerated in an aqueous solution, the compatibility with the hydrogel matrix and the interfacial bonding force are insufficient. Therefore, it is an urgent problem to enhance the compatibility and the interface bonding strength between the carbon-based material and the hydrogel and to improve the electrical conductivity of the composite hydrogel.
Disclosure of Invention
The invention aims to provide a preparation method of tannic acid functionalized carbon nanotube/graphene composite hydrogel, which solves the problem of uneven dispersion of carbon nanotubes and graphene in a gel matrix.
The technical scheme adopted by the invention is that the preparation method of the tannic acid functionalized carbon nanotube/graphene composite hydrogel is implemented according to the following steps:
step 1, preparing graphene;
step 2: adding the carbon nano tube, the tannic acid and the graphene prepared in the step 1 into a solvent for dissolving, uniformly stirring, and performing ultrasonic treatment to obtain a solution b; heating the solution b in an oil bath for reaction, performing suction filtration, washing with deionized water to be neutral, and performing cold drying to obtain the tannic acid functionalized carbon nanotube/graphene;
step 3, adding polyvinyl alcohol into deionized water, stirring to obtain a suspension, heating the suspension in an oil bath, and mechanically stirring to obtain a solution c;
and 4, adding the tannic acid functionalized carbon nanotube/graphene into deionized water, uniformly stirring to obtain a solution d, mixing the solution d with the solution c prepared in the step 3, performing oil bath heating and stirring to obtain a mixed solution, pouring the mixed solution into a polytetrafluoroethylene mold, and performing freeze thawing circulation to obtain the tannic acid functionalized carbon nanotube/graphene composite hydrogel with high conductivity and excellent mechanical properties.
The present invention is also characterized in that,
in the step 1, the method specifically comprises the following steps:
adding graphene oxide into a deionized water solution, stirring and then carrying out ultrasonic treatment to obtain a solution a, adding L-ascorbic acid into the solution a, uniformly stirring, and then heating in a water bath; washing with deionized water, and performing suction filtration to obtain a solid substance; and (3) carrying out cold drying on the solid matter, carrying out coarse grinding after the cold drying, and then carrying out fine grinding by using agate to obtain black powdery graphene.
The mass ratio of the graphene oxide to the L-ascorbic acid is 1: 8-10, wherein the ultrasonic power is 115-125W, the ultrasonic time is 1-2 h, the water bath heating temperature is 70-85 ℃, and the water bath heating time is 2-4 h; during cold drying, the mixture is frozen in a cold trap at the temperature of-20 to-25 ℃ for 10 to 12 hours and then dried for 24 to 48 hours.
In the step 2, the carbon nano tube is a single-wall carbon nano tube or a multi-wall carbon nano tube; the mass ratio of the graphene to the carbon nano tube to the tannic acid is 1: 2: 3 to 5.
In the step 2, the ultrasonic power is 120-135W, and the ultrasonic time is 30-90 min; the heating temperature of the oil bath is 85 ℃, and the heating time of the oil bath is 8 hours; during cold drying, the mixture is frozen in a cold trap at the temperature of-20 to-25 ℃ for 10 to 12 hours and then dried for 24 to 48 hours.
In the step 3, the mass fraction of the polyvinyl alcohol suspension is 6-9%, the oil bath heating temperature is 95 ℃, and the oil bath heating time is 3-5 hours.
In the step 4, the heating temperature of the oil bath is 90 ℃, the heating time of the oil bath is 1-3 h, and the stirring speed is 500-1500 r/min.
In the step 4, when freeze-thaw cycling is carried out, the freezing temperature is-20 to-30 ℃, the freezing time is 10 to 15 hours, the thawing time is 3 to 6 hours, and the number of freeze-thaw cycling times is 2 to 5.
The tannin functionalized carbon nanotube/graphene composite hydrogel disclosed by the invention has the beneficial effects that the dispersibility of the conductive filler in the gel matrix is enhanced, the conductive performance and the mechanical performance of the hydrogel are improved, and the prepared nano composite hydrogel can be used for a pressure/strain sensor. In addition, the modified material used by the method is green and natural, meets the requirement of green environmental protection, has simple preparation process, is easy to build an operation platform, can improve the production efficiency and reduce the production cost.
Drawings
FIG. 1 is a scanning electron micrograph of a pure polyvinyl alcohol hydrogel;
FIG. 2 is a scanning electron micrograph of a cross section of a pure polyvinyl alcohol hydrogel;
FIG. 3 is a scanning electron micrograph of TA-CNT/GE composite hydrogel with conductive filler added;
FIG. 4 is a scanning electron micrograph of the cross section of the TA-CNT/GE composite hydrogel with the conductive filler added.
Detailed Description
The present invention will be described in detail with reference to the following detailed description and accompanying drawings.
The invention relates to a preparation method of tannic acid functionalized carbon nanotube/graphene composite hydrogel, which is implemented according to the following steps:
step 1, preparing graphene
Adding graphene oxide into a deionized water solution, stirring and then performing ultrasonic treatment to obtain a solution a, adding L-ascorbic acid into the solution a, uniformly stirring, and then heating in a water bath; washing with deionized water, and performing suction filtration to obtain a solid substance; the solid matter is subjected to cold drying, coarse grinding is carried out after the cold drying, and then fine grinding is carried out on agate, so that black powdery graphene is obtained;
wherein the mass ratio of the graphene oxide to the L-ascorbic acid is 1: 8-10, wherein the ultrasonic power is 115-125W, the ultrasonic time is 1-2 h, the water bath heating temperature is 70-85 ℃, and the water bath heating time is 2-4 h;
during cold drying, firstly freezing the mixture in a cold trap at the temperature of between 20 ℃ below zero and 25 ℃ below zero for 10 to 12 hours, and then drying the mixture for 24 to 48 hours;
step 2: preparing tannin functionalized carbon nanotube/graphene (TGC);
adding the carbon nano tube, the tannic acid and the graphene powder prepared in the step 1 into a solvent for dissolving, uniformly stirring, and performing ultrasonic treatment to obtain a solution b; pouring the solution b into a round-bottom flask, carrying out heating reaction in an oil bath, after the reaction is finished, carrying out suction filtration, washing with deionized water to be neutral, and carrying out cold drying to obtain the tannic acid functionalized carbon nanotube/graphene;
wherein the carbon nano tube is a single-wall carbon nano tube or a multi-wall carbon nano tube;
the mass ratio of the graphene to the carbon nano tube to the tannic acid is 1: 2: 3-5;
the ultrasonic power is 120-135W, and the ultrasonic time is 30-90 min;
the heating temperature of the oil bath is 85 ℃, and the heating time of the oil bath is 8 hours;
during cold drying, firstly freezing the mixture in a cold trap at the temperature of between 20 ℃ below zero and 25 ℃ below zero for 10 to 12 hours, and then drying the mixture for 24 to 48 hours;
step 3, adding polyvinyl alcohol into deionized water, magnetically stirring to obtain a suspension, pouring the suspension into a round-bottom flask, heating in an oil bath, and mechanically stirring to obtain a solution c;
wherein the mass fraction of the polyvinyl alcohol suspension is 6-9%, the oil bath heating temperature is 95 ℃, and the oil bath heating time is 3-5 h;
step 4, adding tannic acid functionalized carbon nano tube/graphene (TGC) into deionized water, uniformly stirring to obtain a solution d, mixing the solution d with the solution c prepared in the step 3, pouring the mixture into a round-bottom flask, heating in an oil bath, stirring to obtain a mixed solution, pouring the mixed solution into a Polytetrafluoroethylene (PTFE) mold, and performing freeze-thaw cycling to obtain the tannic acid functionalized carbon nano tube/graphene composite hydrogel with high conductivity and excellent mechanical properties;
wherein the oil bath heating temperature is 90 ℃, the oil bath heating time is 1-3 h, and the stirring speed is 500-1500 r/min;
and (3) performing freeze-thaw cycling at the freezing temperature of-20 to-30 ℃, for 10 to 15 hours, for 3 to 6 hours, and for 2 to 5 times.
FIG. 1 is a scanning electron micrograph of a pure polyvinyl alcohol hydrogel, from which FIG. 1 it can be seen that the well dispersed TA-CNT/GE is tightly embedded in the polyvinyl alcohol matrix. This indicates a strong interfacial bond between the filler and the polyvinyl alcohol matrix. FIG. 2 is a scanning electron micrograph of a cross section of a pure polyvinyl alcohol hydrogel, showing a relatively regular and smooth fracture surface. FIGS. 3 and 4 are scanning electron micrographs of the cross section of the TA-CNT/GE nanocomposite hydrogel with the conductive filler added thereto, and it was observed that the cross section became relatively rough after the TA-CNT/GE addition. This is due to the presence of the TA-CNT/GE nanofiller which results from crack propagation and dissipation of the energy of crack propagation. The results show that the TA-CNT/GE doped nano filler has great success in improving the strength and toughness of the polyvinyl alcohol hydrogel.
Example 1
The invention discloses a preparation method of tannin functionalized carbon nanotube/graphene composite hydrogel, which is implemented according to the following steps:
step 1, dissolving 150mg of graphene oxide in 100mL of deionized water solution, uniformly stirring, performing 120W ultrasonic treatment for 20min to obtain a solution a, adding 1.5g L-ascorbic acid into the solution a, uniformly stirring, and heating in a water bath at 80 ℃ for 4 h; then carrying out suction filtration and deionized water washing to be neutral to obtain a solid; putting the obtained solid into a cold dryer, freezing the solid in a cold trap for 12 hours, then drying the solid for 48 hours, and grinding the solid to obtain black powdery graphene;
step 2, adding 50mg of graphene powder prepared in the step 1, 100mg of carbon nano tubes and 150mg of tannic acid into deionized water for dissolving, uniformly stirring, and performing 135W ultrasonic treatment for 30min to obtain a solution b; pouring the solution b into a round-bottom flask, and then heating for 8 hours in an oil bath at 90 ℃; after the reaction is finished, performing suction filtration and deionized water washing on the product until the product is neutral, putting the obtained product into a cold drying machine, freezing the product in a cold trap for 12 hours, and then performing cold drying for 48 hours to obtain the tannin functionalized carbon nanotube/graphene;
step 3, 5.4g polyvinyl alcohol was added to 60mL deionized water, stirred magnetically for 1h, allowed to foam to give a suspension, which was poured into a round bottom flask, stirred mechanically at 1000r/min and placed in a 95 ℃ oil bath for 3h to give solution c.
And 4, adding 50mg of tannic acid functionalized carbon nanotube/graphene (TGC) into 50mL of deionized water, uniformly stirring to obtain a solution d, mixing 5mL of the solution d with the solution c prepared in the step 3, pouring the mixture into a round-bottom flask, heating in an oil bath at 90 ℃ for 2 hours, magnetically stirring at the speed of 1500r/min to obtain a mixed solution a, pouring the mixed solution a into a Polytetrafluoroethylene (PTFE) mold, performing freeze-thaw cycle, freezing at-24 ℃ for 12 hours, thawing at room temperature for 3 hours, and performing freeze-thaw cycle for 3 times to obtain the tannic acid functionalized carbon nanotube/graphene nano composite hydrogel with high conductivity and excellent mechanical property.
Example 2
The invention relates to a preparation method of tannic acid functionalized carbon nanotube/graphene composite hydrogel, which is implemented according to the following steps:
step 1, dissolving 150mg of graphene oxide in 100mL of deionized water solution, uniformly stirring, performing 120W ultrasonic treatment for 20min to obtain a solution a, adding 1.5g L-ascorbic acid into the solution a, uniformly stirring, and heating in a water bath at 80 ℃ for 4 h; then carrying out suction filtration and deionized water washing to be neutral to obtain a solid; putting the obtained solid into a freeze-drying machine, freezing the solid in a cold trap for 12 hours, and then freeze-drying the solid for 48 hours. Grinding to obtain black powdery graphene;
step 2, adding 50mg of the graphene powder prepared in the step 1, 100mg of the carbon nano tube and 250mg of tannic acid into deionized water for dissolving, uniformly stirring, and performing 135W ultrasonic treatment for 30min to obtain a solution b; pouring the solution b into a round-bottom flask, and then heating for 8 hours in an oil bath at 90 ℃; after the reaction is finished, performing suction filtration and deionized water washing on the product until the product is neutral, putting the obtained product into a cold drying machine, freezing the product in a cold trap for 12 hours, and then cooling and drying the product for 48 hours to obtain the tannin functionalized carbon nano tube/graphene;
step 3, 5.4g polyvinyl alcohol is added to 60mL deionized water, magnetic stirring is carried out for 1h, foaming is carried out to obtain a suspension, the suspension is poured into a round bottom flask, suspension a is mechanically stirred at the speed of 1000r/min and placed in a 95 ℃ oil bath for 3h to obtain solution c.
And 4, step 4: adding 50mg of tannic acid functionalized carbon nanotube/graphene (TGC) into 50mL of deionized water, uniformly stirring to obtain a solution d, mixing 5mL of the solution d with the solution c prepared in the step 3, pouring the mixture into a round-bottomed flask, heating the mixture in an oil bath at 90 ℃ for 2 hours, magnetically stirring at a speed of 1500r/min to obtain a mixed solution a, pouring the mixed solution a into a Polytetrafluoroethylene (PTFE) mold, performing freeze-thaw cycle, freezing the mixed solution at-24 ℃ for 12 hours, then thawing the mixed solution at room temperature for 3 hours, and performing freeze-thaw cycle for 3 times to obtain the tannic acid functionalized carbon nanotube/graphene nano composite hydrogel with high conductivity and excellent mechanical property.
Example 3
The invention discloses a preparation method of tannin functionalized carbon nanotube/graphene composite hydrogel, which is implemented according to the following steps:
step 1, dissolving 150mg of graphene oxide in 100mL of deionized water solution, uniformly stirring, performing 120W ultrasonic treatment for 20min to obtain a solution a, adding 1.5g L-ascorbic acid into the solution a, uniformly stirring, and heating in a water bath at 80 ℃ for 4 h; then carrying out suction filtration and deionized water washing to be neutral to obtain a solid a; putting the obtained solid a into a cold drying machine, freezing the solid a in a cold trap for 12 hours, then drying the solid a in a cold drying mode for 48 hours, and grinding the solid a to obtain black powdery graphene;
step 2, adding 50mg of the graphene powder prepared in the step 1, 100mg of the carbon nano tube and 450mg of tannic acid into deionized water for dissolving, uniformly stirring, and performing 135W ultrasonic treatment for 30min to obtain a solution b; pouring the solution b into a round-bottom flask, and then heating for 8 hours in an oil bath at 90 ℃; after the reaction is finished, performing suction filtration and deionized water washing on the product until the product is neutral, putting the obtained product into a cold drying machine, freezing the product in a cold trap for 12 hours, and then performing cold drying for 48 hours to obtain the tannin functionalized carbon nanotube/graphene;
step 3, adding 5.4g of polyvinyl alcohol into 60mL of deionized water, stirring for 1h by magnetic force, carrying out foaming to obtain suspension a, pouring the suspension a into a round-bottom flask, mechanically stirring the suspension a at the speed of 1000r/min, and placing the suspension a in an oil bath at 95 ℃ for 3h to obtain solution c.
And 4, step 4: adding 50mg of tannic acid functionalized carbon nanotube/graphene (TGC) into 50mL of deionized water, uniformly stirring to obtain a solution d, mixing 5mL of the solution d with the solution c prepared in the step 3, pouring the mixture into a round-bottomed flask, heating the mixture in an oil bath at 90 ℃ for 2 hours, magnetically stirring at a speed of 1500r/min to obtain a mixed solution a, pouring the mixed solution a into a Polytetrafluoroethylene (PTFE) mold, performing freeze-thaw cycle, freezing the mixed solution at-24 ℃ for 12 hours, then thawing the mixed solution at room temperature for 3 hours, and performing freeze-thaw cycle for 3 times to obtain the tannic acid functionalized carbon nanotube/graphene nano composite hydrogel with high conductivity and excellent mechanical property.
Example 4
The invention relates to a preparation method of tannic acid functionalized carbon nanotube/graphene composite hydrogel, which is implemented according to the following steps:
step 1, dissolving 150mg of graphene oxide in 100mL of deionized water solution, uniformly stirring, performing 120W ultrasonic treatment for 20min to obtain a solution a, adding 1.5g L-ascorbic acid into the solution a, uniformly stirring, and heating in a water bath at 80 ℃ for 4 h; then carrying out suction filtration and deionized water washing to be neutral to obtain a solid a; and (3) putting the obtained solid a into a freeze-drying machine, freezing the solid a in a cold trap for 12 hours, and then freeze-drying the solid a for 48 hours. Grinding to obtain black powdery graphene;
step 2, adding 50mg of the graphene powder prepared in the step 1, 100mg of the carbon nano tube and 250mg of tannic acid into deionized water for dissolving, uniformly stirring, and performing 135W ultrasonic treatment for 30min to obtain a solution b; pouring the solution b into a round-bottom flask, and then heating for 8 hours in an oil bath at 90 ℃; after the reaction is finished, performing suction filtration and deionized water washing on the product until the product is neutral, putting the obtained product into a cold drying machine, freezing the product in a cold trap for 12 hours, and then performing cold drying for 48 hours to obtain the tannin functionalized carbon nanotube/graphene;
step 3, add 5.4g polyvinyl alcohol to 60mL deionized water, stir magnetically for 1h, bubble to give suspension a, pour suspension a into round bottom flask, stir mechanically at 1000r/min and put in 95 deg.C oil bath for 3h to give solution c.
And 4, step 4: adding 150mg of tannic acid functionalized carbon nanotube/graphene (TGC) into 50mL of deionized water, uniformly stirring to obtain a solution d, mixing 5mL of the solution d with the solution c prepared in the step 3, pouring the mixture into a round-bottomed flask, heating the mixture in an oil bath at 90 ℃ for 2 hours, magnetically stirring at a speed of 1500r/min to obtain a mixed solution a, pouring the mixed solution a into a Polytetrafluoroethylene (PTFE) mold, performing freeze-thaw cycle, freezing the mixed solution at-24 ℃ for 12 hours, then thawing the mixed solution at room temperature for 3 hours, and performing freeze-thaw cycle for 3 times to obtain the tannic acid functionalized carbon nanotube/graphene nano composite hydrogel with high conductivity and excellent mechanical property.
Example 5
The invention relates to a preparation method of tannic acid functionalized carbon nanotube/graphene composite hydrogel, which is implemented according to the following steps:
step 1, dissolving 150mg of graphene oxide in 100mL of deionized water solution, uniformly stirring, performing 120W ultrasonic treatment for 20min to obtain a solution a, adding 1.5g L-ascorbic acid into the solution a, uniformly stirring, and heating in a water bath at 80 ℃ for 4 h; then carrying out suction filtration and deionized water washing until the solution is neutral to obtain a solid a; and (3) putting the obtained solid a into a freeze-drying machine, freezing the solid a in a cold trap for 12 hours, and then freeze-drying the solid a for 48 hours. Grinding to obtain black powdery graphene;
step 2, adding 50mg of graphene powder prepared in the step 1, 100mg of carbon nano tubes and 250mg of tannic acid into deionized water for dissolving, uniformly stirring, and performing 135W ultrasonic treatment for 30min to obtain a solution b; pouring the solution b into a round-bottom flask, and then heating for 8 hours in an oil bath at 90 ℃; after the reaction is finished, performing suction filtration and deionized water washing on the product until the product is neutral, putting the obtained product into a cold drying machine, freezing the product in a cold trap for 12 hours, and then performing cold drying for 48 hours to obtain the tannin functionalized carbon nanotube/graphene;
step 3, adding 5.4g of polyvinyl alcohol into 60mL of deionized water, stirring for 1h by magnetic force, carrying out foaming to obtain suspension a, pouring the suspension a into a round-bottom flask, mechanically stirring the suspension a at the speed of 1000r/min, and placing the suspension a in an oil bath at 95 ℃ for 3h to obtain solution c.
And 4, step 4: adding 250mg of tannic acid functionalized carbon nanotube/graphene (TGC) into 50mL of deionized water, uniformly stirring to obtain a solution d, mixing 5mL of the solution d with the solution c prepared in the step 3, pouring the mixture into a round-bottom flask, heating in an oil bath at 90 ℃ for 2h, magnetically stirring at a speed of 1500r/min to obtain a mixed solution a, pouring the mixed solution a into a Polytetrafluoroethylene (PTFE) mold, performing freeze-thaw cycle, freezing at-24 ℃ for 12h, then thawing at room temperature for 3h, and performing freeze-thaw cycle for 3 times to obtain the tannic acid functionalized carbon nanotube/graphene nano composite hydrogel with high conductivity and excellent mechanical property.
Example 6
The invention relates to a preparation method of tannic acid functionalized carbon nanotube/graphene composite hydrogel, which is implemented according to the following steps:
step 1, dissolving 150mg of graphene oxide in 100mL of deionized water solution, uniformly stirring, performing 120W ultrasonic treatment for 20min to obtain a solution a, adding 1.5g L-ascorbic acid into the solution a, uniformly stirring, and heating in a water bath at 80 ℃ for 4 h; then carrying out suction filtration and deionized water washing to be neutral to obtain a solid a; and (4) putting the obtained solid a into a freeze drying machine, freezing the solid a in a cold trap for 12 hours, and then carrying out freeze drying for 48 hours. Grinding to obtain black powdery graphene;
step 2, adding 50mg of the graphene powder prepared in the step 1, 100mg of the carbon nano tube and 250mg of tannic acid into deionized water for dissolving, uniformly stirring, and performing 135W ultrasonic treatment for 30min to obtain a solution b; pouring the solution b into a round-bottom flask, and then heating for 8 hours in an oil bath at 90 ℃; after the reaction is finished, performing suction filtration and deionized water washing on the product until the product is neutral, putting the obtained product into a cold drying machine, freezing the product in a cold trap for 12 hours, and then performing cold drying for 48 hours to obtain the tannin functionalized carbon nanotube/graphene;
step 3, adding 5.4g of polyvinyl alcohol into 60mL of deionized water, stirring for 1h by magnetic force, carrying out foaming to obtain suspension a, pouring the suspension a into a round-bottom flask, mechanically stirring the suspension a at the speed of 1000r/min, and placing the suspension a in an oil bath at 95 ℃ for 3h to obtain solution c.
And 4, step 4: adding 500mg of tannic acid functionalized carbon nanotube/graphene (TGC) into 50mL of deionized water, uniformly stirring to obtain a solution d, mixing 5mL of the solution d with the solution c prepared in the step 3, pouring the mixture into a round-bottom flask, heating in an oil bath at 90 ℃ for 2h, magnetically stirring at a speed of 1500r/min to obtain a mixed solution a, pouring the mixed solution a into a Polytetrafluoroethylene (PTFE) mold, performing freeze-thaw cycle, freezing at-24 ℃ for 12h, then thawing at room temperature for 3h, and performing freeze-thaw cycle for 3 times to obtain the tannic acid functionalized carbon nanotube/graphene nano composite hydrogel with high conductivity and excellent mechanical property.
The properties of the tannin functionalized carbon nanotube/graphene nanocomposite hydrogel prepared in the embodiment of the present invention were measured, and the results are shown in tables 1 and 2:
TABLE 1 Electrical Properties of tannin functionalized carbon nanotubes/graphene (TGC)
TABLE 2 elongation at break of tannin functionalized carbon nanotube/graphene composite hydrogels
| Sample name | Elongation at Break (%) |
| Example 1 | 290 |
| Example 4 | 300 |
| Example 5 | 270 |
| Example 6 | 250 |
| Unmodified carbon nanotube/graphene nanocomposite hydrogel | 206 |
As can be seen from table 1 conductivity test of tannic acid functionalized carbon nanotubes/graphene (TGC), carbon nanotube/graphene powder: tannic Acid (TA) is 3: and 5, the measured conductivity is the highest, namely the tannin functionalized carbon nanotube/graphene has the best dispersibility in an aqueous solution at the ratio, so the TGC is used as a conductive filler.
As shown in Table 2, the tannic acid functionalized carbon nanotube/graphene nanocomposite hydrogel prepared by the invention has high elongation at break and good tensile property. The mechanical properties of example 5 and example 6 are slightly reduced compared with those of other examples, which is probably caused by slight agglomeration in the composite material due to the higher mass fraction of the tannin-functionalized carbon nanotubes/graphene in example 5 and example 6.
The hydrogel disclosed by the invention can be uniformly dispersed in an aqueous solution, the TA functionalized CNT/GE is doped into a polyvinyl alcohol matrix and can be uniformly dispersed in a water-soluble polyvinyl alcohol matrix, so that the hydrogel is endowed with excellent conductivity, and meanwhile, the TA functionalized CNT/GE and the polyvinyl alcohol have stronger interface bonding force, so that the conductivity of the hydrogel matrix is enhanced.
The invention changes the performance of the hydrogel by adding the conductive filler, and the reasons are as follows: graphene (GE) and Carbon Nanotubes (CNT) have excellent conductivity; the GE is obtained by reducing GO through L-ascorbic acid, although the conductivity is increased, graphene has hydrophobicity and is easy to agglomerate in an aqueous solution, Van der Waals force among CNTs enables the CNTs to agglomerate easily, and tannic acid TA is introduced to serve as a dispersing agent. Secondly, because TA has a hydrophobic aromatic ring similar to a conjugated carbon nano material, the TA has the effect of a conjugated pi bond on a GE sheet layer, is inserted between the GE sheet layers and obstructs the stacking of GE; the adsorption capacity of TA increases the steric repulsion force, thereby balancing the van der waals forces between CNTs, enabling CNTs to be uniformly dispersed in water. In addition, TA functionalized CNT/GE showed stronger adsorption capacity to polyvinyl alcohol substrate due to hydrogen bond and electrostatic interaction. Therefore, the TA functionalized CNT/GE is introduced to effectively improve the conductivity of the hydrogel and effectively enhance the mechanical property of the hydrogel.
Claims (8)
1. The preparation method of the tannin functionalized carbon nanotube/graphene composite hydrogel is characterized by comprising the following steps:
step 1, preparing graphene;
step 2: adding the carbon nano tube, the tannic acid and the graphene prepared in the step 1 into a solvent for dissolving, uniformly stirring, and performing ultrasonic treatment to obtain a solution b; heating the solution b in an oil bath for reaction, performing suction filtration, washing with deionized water to be neutral, and performing cold drying to obtain the tannic acid functionalized carbon nanotube/graphene;
step 3, adding polyvinyl alcohol into deionized water, stirring to obtain a suspension, heating the suspension in an oil bath, and mechanically stirring to obtain a solution c;
and 4, adding the tannic acid functionalized carbon nanotube/graphene into deionized water, uniformly stirring to obtain a solution d, mixing the solution d with the solution c prepared in the step 3, performing oil bath heating and stirring to obtain a mixed solution, pouring the mixed solution into a polytetrafluoroethylene mold, and performing freeze thawing circulation to obtain the tannic acid functionalized carbon nanotube/graphene composite hydrogel with high conductivity and excellent mechanical properties.
2. The method for preparing the tannin functionalized carbon nanotube/graphene composite hydrogel according to claim 1, wherein the step 1 specifically comprises:
adding graphene oxide into a deionized water solution, stirring and then carrying out ultrasonic treatment to obtain a solution a, adding L-ascorbic acid into the solution a, uniformly stirring, and then heating in a water bath; washing with deionized water, and performing suction filtration to obtain a solid substance; and (3) carrying out cold drying on the solid matter, carrying out coarse grinding after the cold drying, and then carrying out fine grinding by using agate to obtain black powdery graphene.
3. The method for preparing the tannin functionalized carbon nanotube/graphene composite hydrogel according to claim 2, wherein the mass ratio of the graphene oxide to the L-ascorbic acid is 1: 8-10, wherein the ultrasonic power is 115-125W, the ultrasonic time is 1-2 h, the water bath heating temperature is 70-85 ℃, and the water bath heating time is 2-4 h; during cold drying, the mixture is frozen in a cold trap at the temperature of-20 to-25 ℃ for 10 to 12 hours and then dried for 24 to 48 hours.
4. The method for preparing the tannin functionalized carbon nanotube/graphene composite hydrogel according to claim 1, wherein in the step 2, the carbon nanotubes are single-walled carbon nanotubes or multi-walled carbon nanotubes; the mass ratio of the graphene to the carbon nano tube to the tannic acid is 1: 2: 3 to 5.
5. The method for preparing the tannin functionalized carbon nanotube/graphene composite hydrogel according to claim 1, wherein in the step 2, the ultrasonic power is 120-135W, and the ultrasonic time is 30-90 min; the oil bath heating temperature is 85 ℃, and the oil bath heating time is 8 hours; and during cold drying, firstly freezing the mixture in a cold trap at the temperature of between 20 ℃ below zero and 25 ℃ below zero for 10 to 12 hours, and then drying the mixture for 24 to 48 hours.
6. The method for preparing the tannin functionalized carbon nanotube/graphene composite hydrogel according to claim 1, wherein in the step 3, the mass fraction of the polyvinyl alcohol suspension is 6-9%, the oil bath heating temperature is 95 ℃, and the oil bath heating time is 3-5 h.
7. The method for preparing the tannin functionalized carbon nanotube/graphene composite hydrogel according to claim 1, wherein in the step 4, the oil bath heating temperature is 90 ℃, the oil bath heating time is 1-3 h, and the stirring speed is 500-1500 r/min.
8. The method for preparing the tannic acid functionalized carbon nanotube/graphene composite hydrogel according to claim 1, wherein in the step 4, when freeze-thaw cycles are performed, the freezing temperature is-20 to-30 ℃, the freezing time is 10 to 15 hours, the thawing time is 3 to 6 hours, and the number of the freeze-thaw cycles is 2 to 5.
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