CN114516966B - Carbon nano tube-based conductive hydrogel and preparation method thereof - Google Patents

Carbon nano tube-based conductive hydrogel and preparation method thereof Download PDF

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CN114516966B
CN114516966B CN202011314500.4A CN202011314500A CN114516966B CN 114516966 B CN114516966 B CN 114516966B CN 202011314500 A CN202011314500 A CN 202011314500A CN 114516966 B CN114516966 B CN 114516966B
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冯亮
支慧
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Dalian Institute of Chemical Physics of CAS
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    • C08J3/02—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques
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    • 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
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Abstract

The application discloses a carbon nano tube-based conductive hydrogel and a preparation method thereof, wherein the composition components of the carbon nano tube-based conductive hydrogel at least comprise: modified carbon nanotubes, polyvinyl alcohol, polysaccharide and ionic liquid; the ionic liquid is imidazole ionic liquid. By introducing the modified carbon nano tube, the modified carbon nano tube has good water dispersibility, high conductivity and good thermal stability, so that not only can the excellent conductivity be provided for the conductive hydrogel, but also the mechanical property of the conductive hydrogel can be improved; by introducing the ionic liquid and the polysaccharide, the toughness of the hydrogel is improved. The ionic liquid not only can increase the dispersibility of the polysaccharide in the hydrogel, but also can provide conductivity for the hydrogel. Meanwhile, the carbon nano tube-based conductive hydrogel is prepared by adopting a spraying method and a circulating freezing-thawing method, and the preparation method is convenient to operate and simple and feasible.

Description

Carbon nano tube-based conductive hydrogel and preparation method thereof
Technical Field
The application relates to a carbon nano tube-based conductive hydrogel and a preparation method thereof, belonging to the field of organic gel preparation.
Background
Conductive hydrogels are a class of conductive materials that have a three-dimensional network structure, swell in water, and are insoluble. The conductive hydrogel is widely applied to the fields of flexible electronics, biosensing, biomedical and the like by virtue of good conductivity. However, hydrogels prepared from organic crosslinkers have poor mechanical properties and conductivity, greatly limiting the development of electrically conductive hydrogels. Therefore, it is particularly important to select a functionalized crosslinked material that has both good crosslinking properties and excellent electrical conductivity.
Carbon nanotubes are unique one-dimensional nano materials, have excellent mechanical properties, electrical conductivity and thermodynamic properties, and are considered as more ideal reinforcing materials for polymer composites by virtue of the excellent mechanical properties. Therefore, the carbon nano tube can be used as a multifunctional crosslinking agent to prepare the composite conductive hydrogel. The carbon nano tube is introduced into the polymer composite hydrogel, so that not only can the conductivity of the composite hydrogel be endowed, but also the mechanical property of the composite hydrogel can be improved. In recent years, research on carbon nanotube-based conductive hydrogels has been advanced to some extent, but the low dispersibility of carbon nanotubes in hydrogels makes the improvement of the mechanical properties of polymer hydrogels limited, so the preparation of carbon nanotube-based conductive hydrogels with high mechanical strength has been recently reported.
Disclosure of Invention
The application provides a carbon nano tube-based conductive hydrogel and a preparation method thereof, which solve the problem that the traditional conductive hydrogel is poor in mechanical property and conductive property due to the introduction of an organic cross-linking agent.
According to one aspect of the present application, there is provided a carbon nanotube-based conductive hydrogel, the composition of which includes at least: modified carbon nanotubes, polyvinyl alcohol, polysaccharide and ionic liquid;
the ionic liquid is imidazole ionic liquid.
Optionally, the mass ratio of polyvinyl alcohol to polysaccharide is 1:0.5-5;
the mass ratio of the polysaccharide to the ionic liquid is 1:50-500;
the mass ratio of the modified carbon nano tube to the ionic liquid is 1:20-200.
Specifically, the lower mass ratio limit of polyvinyl alcohol to polysaccharide may be independently selected from 1:0.5, 1:1, 1:1.5, 1:2, 1:2.5; the upper mass ratio limit of polyvinyl alcohol to polysaccharide may be independently selected from 1:3, 1:3.5, 1:4, 1:4.5, 1:5.
Specifically, the lower mass ratio limit of polysaccharide to ionic liquid may be independently selected from 1:50, 1:100, 1:150, 1:200, 1:250; the upper mass ratio limit of the polysaccharide and the ionic liquid can be independently selected from 1:300, 1:350, 1:400, 1:450 and 1:500.
Specifically, the lower mass ratio limit of the modified carbon nanotube and the ionic liquid can be independently selected from 1:20, 1:50, 1:70, 1:100, 1:120; the upper mass ratio limit of the modified carbon nanotube and the ionic liquid can be independently selected from 1:140, 1:150, 1:170, 1:190 and 1:200.
Optionally, the carbon nanotube-based conductive hydrogel further comprises water;
the water content is 50-70 wt%.
The lower limit of the water content of the carbon nanotube-based conductive hydrogel may be independently selected from 50%, 53%, 55%, 57%, 60%; the upper limit of the water content of the carbon nanotube-based conductive hydrogel may be independently selected from 62%, 65%, 67%, 69%, 70%.
Optionally, the polymerization degree of the polyvinyl alcohol is 1600-1800;
specifically, the degree of polymerization of the polyvinyl alcohol may be independently selected from 1600, 1650, 1700, 1750, 1800, or any value between any two of the above ranges.
Optionally, the polysaccharide is at least one selected from chitosan, sodium alginate, agar, and carboxymethyl cellulose; preferably, the polysaccharide is chitosan, and the viscosity of the chitosan is … …;
optionally, the imidazole ionic liquid has a structural formula shown in formula I:
wherein R is 1 Any one selected from alkane groups; r is R 2 Selected from the group consisting of alkyl or alkene groups; preferably, the alkyl group has less than 5 carbon atoms; the alkylene is vinyl; further preferably, the alkanyl is selected from propyl or butyl;
x is selected from any one of halogens, preferably X is chlorine or bromine.
Optionally, the imidazole ionic liquid is selected from at least one of 1-butyl-3-methylimidazole bromide, 1-butyl-3-methylimidazole chloride, 1-propyl-3-methylimidazole bromide, 1-propyl-3-methylimidazole chloride, 1-vinyl-3-butylimidazole bromide and 1-propyl-3-methylimidazole chloride.
The application is not particularly limited to the carbon nanotubes used, and one skilled in the art can select single-walled carbon nanotubes or multi-walled carbon nanotubes as needed; meanwhile, the modification mode of the carbon nanotubes is not particularly limited, so long as the dispersibility of the carbon nanotubes can be improved, a person skilled in the art can select the modification mode of the carbon nanotubes according to needs, and acidification modification is adopted in the specific implementation process of the application.
According to still another aspect of the present application, the method for preparing a carbon nanotube-based conductive hydrogel at least includes:
spraying a solution I containing modified carbon nano tubes, polysaccharide, ionic liquid and polyvinyl alcohol on a substrate to obtain pre-gel;
and (3) carrying out gelation treatment on the pregel to obtain the carbon nano tube-based conductive hydrogel.
Optionally, the conditions of spraying are:
the spraying air pressure is 5-30 Psi; the spraying speed is 1-15L/min; the spraying distance is 5-10 cm.
In particular, the lower limit of the spray air pressure may be independently selected from 5Psi, 10Psi, 12Psi, 15Psi, 17Psi; the upper limit of the spray air pressure may be independently selected from 20Psi, 22Psi, 25Psi, 27Psi, 30Psi.
Specifically, the lower limit of the spraying speed can be independently selected from 1L/min, 3.5L/min, 5L/min, 6.5L/min, 8L/min; the upper limit of the spraying speed can be independently selected from 10L/min, 11L/min, 12L/min, 13L/min and 15L/min.
Specifically, the lower limit of the spraying distance can be independently selected from 5cm, 5.5cm, 6cm, 6.5cm, 7cm; the upper limit of the spraying distance can be independently selected from 7.5cm, 8cm, 8.5cm, 9cm and 10cm.
Optionally, the gelation treatment comprises: the pre-gel is subjected to a freeze-thaw cycle.
Optionally, the parameters of the freeze-thaw cycle process are:
the freezing temperature is-35 to-20 ℃, and the freezing time is at least 2 hours;
the thawing temperature is 0-25 ℃, and the thawing time is at least 2h;
the number of the cycles is 1 to 50.
Specifically, the lower freezing temperature limit can be independently selected from-35 ℃, -34 ℃, -33 ℃, -32 ℃, -30 ℃; the upper limit of the freezing temperature can be independently selected from-27 ℃, -25 ℃, -24 ℃, -22 ℃, -20 DEG C
Preferably, the freezing time is 2-12 hours; specifically, the lower freezing time limit may be independently selected from: 2h, 3h, 4h, 5h, 6h; the lower freezing time limit may be independently selected from: 7h, 8h, 9h, 10h and 12h.
Specifically, the lower thawing temperature limit may be independently selected from: 0 ℃, 2 ℃, 5 ℃, 8 ℃, 10 ℃; the lower thawing temperature limit may be independently selected from: 12 ℃, 15 ℃, 17 ℃, 20 ℃, 25 ℃.
Preferably, the thawing time is 2-12 hours; specifically, the lower thawing time limit may be independently selected from: 2h, 3h, 4h, 5h, 6h; the lower thawing time limit may be independently selected from: 7h, 8h, 9h, 10h and 12h.
Specifically, the lower limit of the number of cycles may be independently selected from 1, 2, 3, 4, 5; the upper limit of the number of cycles may be independently selected from 30, 35, 40, 45, 50.
Optionally, the solution I is obtained by:
adding the modified carbon nano tube and the polysaccharide into the ionic liquid, and mixing to obtain a homogeneous solution;
and adding a polyvinyl alcohol solution into the homogeneous solution, and mixing to obtain the solution I.
Optionally, the solvent in the polyvinyl alcohol solution is deionized water;
in the polyvinyl alcohol aqueous solution, the mass ratio of the polyvinyl alcohol to the deionized water is 1:10-100.
Specifically, the lower mass ratio of polyvinyl alcohol to deionized water can be independently selected from 1:10, 1:20, 1:30, 1:40, 1:50; the lower mass ratio of polyvinyl alcohol to deionized water can be independently selected from 1:60, 1:70, 1:80, 1:90, 1:100.
Optionally, the mixing temperature of the obtained homogeneous solution is 120-180 ℃;
the mixing temperature of the obtained solution I is 70-100 ℃.
Specifically, the lower limit of the mixing temperature at which a homogeneous solution is obtained may be independently selected from 120 ℃, 125 ℃, 130 ℃, 135 ℃, 140 ℃; the upper limit of the mixing temperature for obtaining a homogeneous solution can be independently selected from 140 ℃, 150 ℃, 160 ℃, 170 ℃ and 180 ℃.
Specifically, the lower limit of the mixing temperature at which the solution I is obtained may be independently selected from 70 ℃, 75 ℃, 80 ℃, 82 ℃, 85 ℃; the upper limit of the mixing temperature at which the solution I is obtained can be independently selected from 88 ℃, 90 ℃, 95 ℃, 97 ℃ and 100 ℃.
In one embodiment of the present application, the preparation method of the carbon nanotube-based conductive hydrogel includes:
s001, modifying the carbon nano tube to obtain a modified carbon nano tube;
s002, adding the modified carbon nano tube and chitosan into the ionic liquid, and mixing to obtain a homogeneous solution;
s003, adding an aqueous solution of polyvinyl alcohol into the homogeneous phase solution, and mixing to obtain a mixed solution;
s004, spraying the mixed solution on a substrate to obtain pre-gel;
s005, carrying out gelation treatment on the pregel to obtain the carbon nano tube-based conductive hydrogel.
The substrate is required to have a smooth surface and to allow easy peeling of the gel obtained by spraying, such as a glass sheet, a polyethylene terephthalate film, a polyvinylidene fluoride film, a polyethylene film, a polypropylene film, etc., preferably a glass sheet is used.
Optionally, step S001 includes at least:
acidifying and modifying the carbon nano tube to obtain a modified carbon nano tube;
preferably, in the acidification modification, the modifier is a mixed solution of concentrated sulfuric acid and concentrated nitric acid;
the acidification modification temperature is 120-180 ℃, and the modification time is 1-10 h.
The concentrated sulfuric acid and the concentrated nitric acid adopted in the method are all commercial reagents, the concentration of the concentrated sulfuric acid is 70-98 wt%, and the concentration of the concentrated nitric acid is 65-70 wt%.
Specifically, the lower limit of the acidification modification temperature can be independently selected from 120 ℃, 125 ℃, 130 ℃, 135 ℃, 140 ℃; the upper limit of the acidification modification temperature can be independently selected from 145 ℃, 150 ℃, 160 ℃, 170 ℃ and 180 ℃.
Optionally, in the mixed solution, the volume ratio of the concentrated sulfuric acid to the concentrated nitric acid is 1-10:1;
the mass volume ratio of the carbon nano tube to the mixed solution is 0.5-1.5 mg/mL.
Specifically, the lower limit of the volume ratio of concentrated sulfuric acid to concentrated nitric acid may be independently selected from 1:1, 2:1, 3:1, 4:1, 5:1; the upper limit of the volume ratio of concentrated sulfuric acid to concentrated nitric acid may be independently selected from 6:1, 7:1, 8:1, 9:1, 10:1.
The beneficial effects that this application can produce include:
1) The application adopts a spraying method and a circulating freezing-thawing method to prepare the carbon nano tube-based conductive hydrogel, and has convenient operation and simple and easy implementation.
2) By introducing the modified carbon nano tube, the modified carbon nano tube has good water dispersibility, high conductivity and good thermal stability, not only can provide excellent conductivity for the conductive hydrogel, but also can improve the mechanical property of the conductive hydrogel.
3) According to the method, the toughness of the hydrogel is improved by introducing the ionic liquid and the polysaccharide. The ionic liquid not only can increase the dispersibility of the polysaccharide in the hydrogel, but also can provide conductivity for the hydrogel.
Drawings
FIG. 1 is a graph showing tensile stress-strain curves of the carbon nanotube-based conductive hydrogels prepared in examples 1 to 4 of the present application;
FIG. 2 is a graph showing the water content of the carbon nanotube-based conductive hydrogels prepared in examples 1 to 4 of the present application at different freeze-thaw cycles.
Detailed Description
The present application is described in detail below with reference to examples, but the present application is not limited to these examples.
Unless otherwise specified, the experimental methods used in the examples of the present application are all conventional methods; unless otherwise indicated, all starting materials in the examples of the present application were purchased commercially.
The multi-wall carbon nano tube adopted in the embodiment of the invention has the manufacturer of Shanghai Ala-Ding >95%, the inner diameter of 3-5nm, the outer diameter of 8-15nm and the length of 50 mu m; polyvinyl alcohol, the manufacturer is Shanghai test, the polymerization degree is 1750+ -50; chitosan, manufacturer is Shanghai Ala, low viscosity, <200 mP.s; the 1-butyl-3-methylimidazole chloride salt is obtained from the institute of chemical and physical of Lanzhou of China academy of sciences and has the purity of 99%.
Example 1
150mg of multi-wall carbon nano tube is taken and dispersed in 200mL of mixed solution of concentrated sulfuric acid (the mass fraction is 70%) and concentrated nitric acid (the mass fraction is 65%), and the volume ratio of the concentrated sulfuric acid to the concentrated nitric acid is 3:1. And (3) reacting the dispersion solution for 3 hours at 140 ℃, cooling, washing with deionized water and ethanol for three times respectively, and vacuum drying at room temperature for 48 hours to obtain the modified multi-wall carbon nano tube. 10mg of modified multiwall carbon nanotubes and 0.02g of chitosan are taken and dissolved in 2g of 1-butyl-3-methylimidazole chloride, and the mixture is stirred for 3 hours at 120 ℃ to obtain a homogeneous solution. 0.04g of polyvinyl alcohol is taken and dissolved in 2g of deionized water, and the mixture is stirred for 3 hours at 90 ℃ to obtain a polyvinyl alcohol aqueous solution. The aqueous solution of polyvinyl alcohol was slowly added to the homogeneous solution at 90℃and stirred for 10 hours to obtain a mixed solution. After cooling, 2g of the mixed solution was added to a spray pen, the spray air pressure was controlled to 10Psi, the spray speed was 10L/min, and the spray distance was 10cm. Spraying the mixed solution on a glass sheet with the side length of 1 x 1cm by using a spray pen for 30s to obtain the pregel. Freezing the pregel at-20 ℃ for 12 hours, thawing at 25 ℃ for 6 hours, and performing 5 times of freeze-thaw cycle treatment to obtain the MWCNT1-H carbon nano tube based conductive hydrogel.
Example 2
150mg of multi-wall carbon nano tube is taken and dispersed in 200mL of mixed solution of concentrated sulfuric acid (the mass fraction is 70%) and concentrated nitric acid (the mass fraction is 65%), and the volume ratio of the concentrated sulfuric acid to the concentrated nitric acid is 3:1. And (3) reacting the dispersion solution for 3 hours at 140 ℃, cooling, washing with deionized water and ethanol for three times respectively, and vacuum drying at room temperature for 48 hours to obtain the modified multi-wall carbon nano tube. 20mg of modified multiwall carbon nanotubes and 0.02g of chitosan are taken and dissolved in 2g of 1-butyl-3-methylimidazole chloride, and the mixture is stirred for 3 hours at 120 ℃ to obtain a homogeneous solution. 0.04g of polyvinyl alcohol is taken and dissolved in 2g of deionized water, and the mixture is stirred for 3 hours at 90 ℃ to obtain a polyvinyl alcohol aqueous solution. The aqueous solution of polyvinyl alcohol was slowly added to the homogeneous solution at 90℃and stirred for 10 hours to obtain a mixed solution. After cooling, 2g of the mixed solution was added to a spray pen, the spray air pressure was controlled to 10Psi, the spray speed was 10L/min, and the spray distance was 10cm. Spraying the mixed solution on a glass sheet with the side length of 1 x 1cm by using a spray pen for 30s to obtain the pregel. Freezing the pregel at-20 ℃ for 12 hours, thawing at 25 ℃ for 6 hours, and performing 5 times of freeze-thaw cycle treatment to obtain the MWCNT2-H carbon nano tube based conductive hydrogel.
Example 3
150mg of multi-wall carbon nano tube is taken and dispersed in 200mL of mixed solution of concentrated sulfuric acid (the mass fraction is 70%) and concentrated nitric acid (the mass fraction is 65%), and the volume ratio of the concentrated sulfuric acid to the concentrated nitric acid is 3:1. And (3) reacting the dispersion solution for 3 hours at 140 ℃, cooling, washing with deionized water and ethanol for three times respectively, and vacuum drying at room temperature for 48 hours to obtain the modified multi-wall carbon nano tube. 40mg of modified multiwall carbon nanotubes and 0.02g of chitosan are taken and dissolved in 2g of 1-butyl-3-methylimidazole chloride, and the mixture is stirred for 3 hours at 120 ℃ to obtain a homogeneous solution. 0.04g of polyvinyl alcohol is taken and dissolved in 2g of deionized water, and the mixture is stirred for 3 hours at 90 ℃ to obtain a polyvinyl alcohol aqueous solution. The aqueous solution of polyvinyl alcohol was slowly added to the homogeneous solution at 90℃and stirred for 10 hours to obtain a mixed solution. After cooling, 2g of the mixed solution was added to a spray pen, the spray air pressure was controlled to 10Psi, the spray speed was 10L/min, and the spray distance was 10cm. Spraying the mixed solution on a glass sheet with the side length of 1 x 1cm by using a spray pen for 30s to obtain the pregel. Freezing the pregel at-20 ℃ for 12 hours, thawing at 25 ℃ for 6 hours, and performing 5 times of freeze-thaw cycle treatment to obtain the MWCNT3-H carbon nano tube based conductive hydrogel.
Example 4
150mg of multi-wall carbon nano tube is taken and dispersed in 200mL of mixed solution of concentrated sulfuric acid (the mass fraction is 70%) and concentrated nitric acid (the mass fraction is 65%), and the volume ratio of the concentrated sulfuric acid to the concentrated nitric acid is 3:1. And (3) reacting the dispersion solution for 3 hours at 140 ℃, cooling, washing with deionized water and ethanol for three times respectively, and vacuum drying at room temperature for 48 hours to obtain the modified multi-wall carbon nano tube. 100mg of modified multiwall carbon nanotubes and 0.02g of chitosan are taken and dissolved in 2g of 1-butyl-3-methylimidazole chloride, and the mixture is stirred for 3 hours at 120 ℃ to obtain a homogeneous solution. 0.04g of polyvinyl alcohol is taken and dissolved in 2g of deionized water, and the mixture is stirred for 3 hours at 90 ℃ to obtain a polyvinyl alcohol aqueous solution. The aqueous solution of polyvinyl alcohol was slowly added to the homogeneous solution at 90℃and stirred for 10 hours to obtain a mixed solution. After cooling, 2g of the mixed solution was added to a spray pen, the spray air pressure was controlled to 10Psi, the spray speed was 10L/min, and the spray distance was 10cm. Spraying the mixed solution on a glass sheet with the side length of 1 x 1cm by using a spray pen for 30s to obtain the pregel. Freezing the pregel at-20 ℃ for 12 hours, thawing at 25 ℃ for 6 hours, and performing 5 times of freeze-thaw cycle treatment to obtain the MWCNT4-H carbon nano tube based conductive hydrogel.
Example 5
150mg of single-walled carbon nanotubes are taken and dispersed in 200mL of mixed solution of concentrated sulfuric acid (the mass fraction is 70%) and concentrated nitric acid (the mass fraction is 65%), and the volume ratio of the concentrated sulfuric acid to the concentrated nitric acid is 1:1. And (3) reacting the dispersion solution for 3 hours at 160 ℃, cooling, washing with deionized water and ethanol for three times respectively, and vacuum drying at room temperature for 48 hours to obtain the modified single-walled carbon nanotube. 100mg of modified single-wall carbon nano tube and 0.02g of sodium alginate are taken and dissolved in 4g of 1-vinyl-3-butyl imidazole bromide, and the mixture is stirred for 2 hours at 160 ℃ to obtain a homogeneous solution. 0.01g of polyvinyl alcohol is taken and dissolved in 1g of deionized water, and the mixture is stirred for 3 hours at 90 ℃ to obtain a polyvinyl alcohol aqueous solution. The aqueous solution of polyvinyl alcohol was slowly added to the homogeneous solution at 70℃and stirred for 12 hours to obtain a mixed solution. After cooling, 2g of the mixed solution reaction solution was added to a spray pen, the spray air pressure was controlled to 15Psi, the spray speed was 15L/min, and the spray distance was 8cm. Spraying the reaction liquid mixed solution on a glass sheet with the side length of 1 x 1cm by using a spray pen for 30s, and obtaining the pre-gel after spraying. Freezing the pregel at-30 ℃ for 10 hours, thawing at 20 ℃ for 8 hours, and performing 5 times of freeze-thaw cycle treatment to obtain the MWCNT5-H carbon nano tube based composite conductive hydrogel.
Example 6
150mg of single-walled carbon nanotubes are taken and dispersed in 200mL of mixed solution of concentrated sulfuric acid (the mass fraction is 70%) and concentrated nitric acid (the mass fraction is 65%), and the volume ratio of the concentrated sulfuric acid to the concentrated nitric acid is 1:1. And (3) reacting the dispersion solution for 3 hours at 160 ℃, cooling, washing with deionized water and ethanol for three times respectively, and vacuum drying at room temperature for 48 hours to obtain the modified single-walled carbon nanotube. 100mg of modified single-wall carbon nano tube and 0.02g of sodium alginate are taken and dissolved in 4g of 1-vinyl-3-butyl imidazole bromide, and the mixture is stirred for 2 hours at 160 ℃ to obtain a homogeneous solution. 0.02g of polyvinyl alcohol is taken and dissolved in 1.5g of deionized water, and the mixture is stirred for 3 hours at 90 ℃ to obtain a polyvinyl alcohol aqueous solution. The aqueous solution of polyvinyl alcohol was slowly added to the homogeneous solution at 70℃and stirred for 12 hours to obtain a mixed solution. After cooling, 2g of the mixed solution reaction solution was added to a spray pen, the spray air pressure was controlled to 15Psi, the spray speed was 15L/min, and the spray distance was 8cm. Spraying the reaction liquid mixed solution on a glass sheet with the side length of 1 x 1cm by using a spray pen for 30s, and obtaining the pre-gel after spraying. Freezing the pregel at-30 ℃ for 10 hours, thawing at 20 ℃ for 8 hours, and performing 5 times of freeze-thaw cycle treatment to obtain the MWCNT6-H carbon nano tube based composite conductive hydrogel.
Example 7
150mg of single-walled carbon nanotubes are taken and dispersed in 200mL of mixed solution of concentrated sulfuric acid (the mass fraction is 70%) and concentrated nitric acid (the mass fraction is 65%), and the volume ratio of the concentrated sulfuric acid to the concentrated nitric acid is 1:1. And (3) reacting the dispersion solution for 3 hours at 160 ℃, cooling, washing with deionized water and ethanol for three times respectively, and vacuum drying at room temperature for 48 hours to obtain the modified single-walled carbon nanotube. 100mg of modified single-walled carbon nanotube and 0.02g of agar are dissolved in 4g of 1-vinyl-3-butylimidazole bromide, and stirred for 2 hours at 160 ℃ to obtain a homogeneous solution. 0.01g of polyvinyl alcohol is taken and dissolved in 1g of deionized water, and the mixture is stirred for 3 hours at 90 ℃ to obtain a polyvinyl alcohol aqueous solution. The aqueous solution of polyvinyl alcohol was slowly added to the homogeneous solution at 70℃and stirred for 12 hours to obtain a mixed solution. After cooling, 2g of the mixed solution reaction solution was added to a spray pen, the spray air pressure was controlled to 15Psi, the spray speed was 15L/min, and the spray distance was 8cm. The reaction mixture was sprayed onto a glass sheet having a side length of 1 x 1cm using a spray pen for 30 seconds. And spraying to obtain the pregel. Freezing the pregel at-30 ℃ for 10 hours, thawing at 20 ℃ for 8 hours, and performing 5 times of freeze-thaw cycle treatment to obtain the MWCNT7-H carbon nano tube based composite conductive hydrogel.
Example 8
150mg of single-walled carbon nanotubes are taken and dispersed in 200mL of mixed solution of concentrated sulfuric acid (the mass fraction is 70%) and concentrated nitric acid (the mass fraction is 65%), and the volume ratio of the concentrated sulfuric acid to the concentrated nitric acid is 1:1. And (3) reacting the dispersion solution for 3 hours at 160 ℃, cooling, washing with deionized water and ethanol for three times respectively, and vacuum drying at room temperature for 48 hours to obtain the modified single-walled carbon nanotube. 100mg of modified single-walled carbon nanotube and 0.02g of cellulose acetate are taken and dissolved in 4g of 1-vinyl-3-butyl imidazole bromide, and the mixture is stirred for 2 hours at 160 ℃ to obtain a homogeneous solution. 0.01g of polyvinyl alcohol is taken and dissolved in 1g of deionized water, and the mixture is stirred for 3 hours at 90 ℃ to obtain a polyvinyl alcohol aqueous solution. Slowly adding the polyvinyl alcohol aqueous solution into the ionic liquid solution containing the multi-wall carbon nano tube and the chitosan in the homogeneous solution at 70 ℃, and stirring for 12 hours to obtain a mixed solution. After cooling, 2g of the mixed solution reaction solution was added to a spray pen, the spray air pressure was controlled to 15Psi, the spray speed was 15L/min, and the spray distance was 8cm. The reaction mixture was sprayed onto a glass sheet having a side length of 1 x 1cm using a spray pen for 30 seconds. And spraying to obtain the pregel. Freezing the pregel at-30 ℃ for 10 hours, thawing at 20 ℃ for 8 hours, and performing 5 times of freeze-thaw cycle treatment to obtain the MWCNT8-H carbon nano tube based composite conductive hydrogel.
Example 9
The modified carbon nanotubes prepared in examples 1 to 8 were subjected to dispersibility test by the following method: respectively dispersing 10mg of carbon nanotubes before and after modification in 1g of deionized water, carrying out ultrasonic treatment for 1h, and standing at room temperature for 24h. Experiments show that after 24 hours of standing, the modified carbon nanotubes can be well dispersed in deionized water, and most of unmodified carbon nanotubes in the deionized water are deposited on the bottom of the bottle. The result shows that the modified carbon nano tube has good water dispersibility.
Example 10
The carbon nanotube-based conductive hydrogels prepared in examples 1 to 4 were tested for tensile properties in an Instron universal tester, with a set tensile speed of 20mm/min. And after the test is finished, corresponding tensile load-displacement data are derived, and are converted into a tensile stress-strain curve by utilizing a formula. The formula for converting displacement data into tensile strain data in tensile testing is:wherein ε is t Represents tensile strain, l t Representing the displacement of the stretching of the spline, and d represents the length of the spline in the initial state of stretching. The formula for converting tensile load into tensile stress data is +.>Wherein sigma t Representing tensile stress, F l Representing tensile load, S represents the cross-sectional area (i.e., width, thickness) of the spline. The specific test results are shown in fig. 1. It can be seen that with the increase of the charge of the modified multiwall carbon nanotubes, the tensile stress of the carbon nanotube-based conductive hydrogels all increased differently, with the tensile stress of MWCNT3-H being the greatest. However, when the dosage of the modified multi-walled carbon nanotubes is 100mg, the strength of the carbon nanotube-based conductive hydrogel is suddenly reduced. This means that, in a certain range, the addition of the modified carbon nanotubes has a good enhancement effect on the tensile properties of the carbon nanotube-based conductive hydrogel, and the addition of too many modified carbon nanotubes causes agglomeration, which results in uneven distribution of the whole gel system and further causes a decrease in the tensile properties of the gel.
Example 11
The carbon nanotube-based conductive hydrogels prepared in examples 1 to 4 were subjected to a water content test, and as shown in FIG. 2, the water content of the MWCNT1-H carbon nanotube-based conductive hydrogel was 67.6%, the water content of the MWCNT2-H carbon nanotube-based conductive hydrogel was 66.7%, the water content of the MWCNT3-H carbon nanotube-based conductive hydrogel was 66.3%, and the water content of the MWCNT4-H carbon nanotube-based conductive hydrogel was 66.5%. According to the test result, in the preparation process of the carbon nano tube-based conductive hydrogel, the different feeding amounts of the modified multi-wall carbon nano tube have little influence on the water content in the gel.
Example 12
The carbon nanotube-based conductive hydrogels prepared in examples 1 to 4 were subjected to resistivity test by: the prepared carbon nano tube-based conductive hydrogel is tested by using a four-probe resistivity tester, the resistivity of the MWCNT1-H carbon nano tube-based conductive hydrogel is 114154 +/-4177 omega cm, the resistivity of the MWCNT2-H carbon nano tube-based conductive hydrogel is 75815 +/-1919 omega cm, the resistivity of the MWCNT3-H carbon nano tube-based conductive hydrogel is 59480 +/-8259 omega cm, the resistivity of the MWCNT4-H carbon nano tube-based conductive hydrogel is 44350 +/-1725 omega cm, the resistivity is the conductivity reciprocal, and the larger the resistivity is, the smaller the conductivity is, which shows that the conductivity of the hydrogel is increased along with the increase of the dosage of the modified carbon nano tube.
The foregoing description is only a few examples of the present application and is not intended to limit the present application in any way, and although the present application is disclosed in the preferred examples, it is not intended to limit the present application, and any person skilled in the art may make some changes or modifications to the disclosed technology without departing from the scope of the technical solution of the present application, and the technical solution is equivalent to the equivalent embodiments.

Claims (8)

1. A method for preparing a carbon nanotube-based conductive hydrogel, which is characterized by at least comprising the following steps:
spraying a solution I containing modified carbon nano tubes, polysaccharide, ionic liquid and polyvinyl alcohol on a substrate to obtain pre-gel;
performing gelation treatment on the pregel to obtain the carbon nano tube-based conductive hydrogel;
the gelation treatment includes: subjecting said pre-gel to a freeze-thaw cycle;
wherein, acidizing and modifying the carbon nano tube to obtain the modified carbon nano tube;
in the acidification modification, the modifier is a mixed solution of concentrated sulfuric acid and concentrated nitric acid;
the ionic liquid is imidazole ionic liquid;
the mass ratio of the modified carbon nano tube to the ionic liquid is 1:50-150;
the mass ratio of the polyvinyl alcohol to the polysaccharide is 1:0.5-5;
the mass ratio of the polysaccharide to the ionic liquid is 1:50-500;
the carbon nano tube-based conductive hydrogel also comprises water;
the water content is 50-70 wt%;
the polymerization degree of the polyvinyl alcohol is 1600-1800;
the polysaccharide is chitosan;
the imidazole ionic liquid is at least one selected from 1-butyl-3-methylimidazole bromide, 1-butyl-3-methylimidazole chloride, 1-propyl-3-methylimidazole bromide, 1-vinyl-3-butylimidazole bromide and 1-propyl-3-methylimidazole chloride.
2. The method for preparing a carbon nanotube-based conductive hydrogel according to claim 1, wherein the spraying conditions are:
the spraying air pressure is 5-30 Psi; the spraying speed is 1-15L/min; the spraying distance is 5-10 cm.
3. The method for preparing a carbon nanotube-based conductive hydrogel according to claim 1, wherein the parameters of the freeze-thaw sequential cycle process are:
the freezing temperature is-35 to-20 ℃ and the freezing time is at least 2h;
the thawing temperature is 0-25 ℃, and the thawing time is at least 2h;
the number of the circulation is 1-50.
4. The method for preparing a carbon nanotube-based conductive hydrogel according to claim 1, wherein the solution I is obtained by:
adding the modified carbon nano tube and the polysaccharide into the ionic liquid, and mixing to obtain a homogeneous solution;
and adding a polyvinyl alcohol solution into the homogeneous solution, and mixing to obtain the solution I.
5. The method for preparing a carbon nanotube-based conductive hydrogel according to claim 4, wherein the solvent in the polyvinyl alcohol solution is deionized water;
in the polyvinyl alcohol solution, the mass ratio of the polyvinyl alcohol to the deionized water is 1:10-100.
6. The method for preparing a carbon nanotube-based conductive hydrogel according to claim 4,
the mixing temperature of the obtained homogeneous solution is 120-180 ℃.
7. The method for preparing a carbon nanotube-based conductive hydrogel according to claim 4,
the mixing temperature of the solution I is 70-100 ℃.
8. A carbon nanotube-based conductive hydrogel prepared by the method for preparing a carbon nanotube-based conductive hydrogel according to any one of claims 1 to 7.
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