CN113651919A - Cold-resistant solar-driven photothermal effect hydrogel electrolyte and preparation and application thereof - Google Patents
Cold-resistant solar-driven photothermal effect hydrogel electrolyte and preparation and application thereof Download PDFInfo
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F261/00—Macromolecular compounds obtained by polymerising monomers on to polymers of oxygen-containing monomers as defined in group C08F16/00
- C08F261/02—Macromolecular compounds obtained by polymerising monomers on to polymers of oxygen-containing monomers as defined in group C08F16/00 on to polymers of unsaturated alcohols
- C08F261/04—Macromolecular compounds obtained by polymerising monomers on to polymers of oxygen-containing monomers as defined in group C08F16/00 on to polymers of unsaturated alcohols on to polymers of vinyl alcohol
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Abstract
The invention relates to a cold-resistant solar-driven photothermal effect hydrogel electrolyte, and preparation and application thereof. The preparation method comprises the following steps: (1) dissolving a high molecular polymer monomer and a cross-linking agent in water, mixing, and reacting to obtain a reaction solution with a high molecular polymer skeleton; (2) adding a transition metal sulfide into the reaction solution to form a dispersion; (3) then putting the dispersion into a mould for freeze drying to form hydrogel; (4) and taking out the freeze-dried hydrogel and soaking the hydrogel in a metal salt solution. Compared with the prior art, the hydrogel obtained by the invention has the characteristics of solar drive, cold resistance, capability of generating photothermal effect and the like, and can be used in a super capacitor.
Description
Technical Field
The invention relates to the field of energy storage, in particular to a cold-resistant solar-driven photothermal effect hydrogel electrolyte and preparation and application thereof.
Background
With the increasing global energy demand, people have put higher demands on the development of efficient energy storage devices. As a novel energy storage device, the super capacitor is widely concerned by people due to high charging and discharging speed and long service life.
The electrolyte comprises liquid electrolyte and solid electrolyte, and is an indispensable component of the super capacitor. The low conductivity of solid electrolytes compared to liquid electrolytes is a major drawback affecting the high performance of energy storage devices. And the polymer hydrogel electrolyte has higher conductivity at room temperature, so that the polymer hydrogel electrolyte gradually becomes a hot spot in the research of high-performance solid-state supercapacitors.
Hydrogel materials, one of the potential electrolytes, have abundant and modifiable physicochemical properties, and have been widely used in various multifunctional electrochemical energy storage devices and electronic devices, including supercapacitors, batteries, triboelectric nanogenerators, electronic skins, and the like. Although hydrogel electrolytes have significant performance advantages due to their water retention, flexibility, adhesion, stretchability, and even self-healing properties, poor low temperature performance still severely hinders further applications of hydrogel electrolyte-based devices and electronic devices in polar and other cold environments.
Therefore, achieving low-temperature anti-freezing performance and improving ionic conductivity of the hydrogel electrolyte are important challenges for expanding the application range of the hydrogel electrolyte. The addition of organic liquids to hydrogels is one method to obtain antifreeze hydrogels. Common organic liquids include ethylene glycol, glycerol, dimethyl sulfoxide, and the like. In these binary/ternary systems, the interaction of the organic liquid with water molecules is believed to be the primary reason for inhibiting the formation of the ice crystal lattice. However, these hydrogels are either not electrically conductive or have low electrical conductivity due to the presence of organic liquids. In addition, the volatility and high pyrophoricity of organic liquids also pose a serious safety hazard to organic hydrogel electrolytes.
Patent CN112898596A discloses a hydrogel electrolyte and its super capacitor, wherein the hydrogel electrolyte is prepared by the following method: under the action of initiator, polymerizing the monomer containing polymer, high molecular polymer and water to form the precursor of hydrogel electrolyte polymer, and soaking the precursor of hydrogel electrolyte polymer in the water solution of inorganic salt and zinc salt. Although the hydrogel electrolyte prepared by the patent has good mechanical strength and flexibility, the hydrogel electrolyte is not disclosed to be used in the photo-thermal field and the cold resistance of hydrogel, so that the corresponding structure and composition design is not carried out to ensure that the hydrogel electrolyte has the corresponding photo-thermal effect and the cold resistance. The cold-resistant solar-driven photothermal effect hydrogel electrolyte is prepared by adopting different methods: polymerizing high molecular polymer monomer under the action of cross-linking agent to form high molecular polymer skeleton, dispersing transition metal sulfide in the high molecular polymer skeleton, freeze drying and soaking in saturated metal salt solution. The invention is different from the patent in that: the photo-thermal material transition metal sulfide is added into a high molecular polymer framework, so that the gel electrolyte has a photo-thermal effect; the concentration of the salt solution added in the invention is saturated solution, and the saturated salt solution can effectively reduce the freezing point of the electrolyte, so that the gel electrolyte has excellent conductivity at low temperature, thereby endowing the gel electrolyte with the cold-resistant characteristic.
Disclosure of Invention
The first purpose of the invention is to provide a cold-resistant solar-driven photothermal effect hydrogel electrolyte.
The purpose of the invention is realized by the following technical scheme:
the utility model provides a cold-resistant solar drive light and heat effect aquogel electrolyte, aquogel electrolyte includes solar drive light and heat material, macromolecular polymer skeleton, cross-linking agent and metal salt solution, solar drive light and heat material is the transition metal sulphide.
The transition metal sulfide comprises molybdenum disulfide (MoS)2) Or tungsten disulfide (WS)2) Molybdenum disulfide (MoS)2) And tungsten disulfide (WS)2) The hydrogel electrolyte can be used as a photo-thermal material and added into a hydrogel polymer framework, and the hydrogel electrolyte can generate a photo-thermal effect under the irradiation of sunlight.
The monomer of the high molecular polymer skeleton comprises one or more of polyvinyl alcohol (PVA), agarose or sodium alginate, and the high molecular polymer skeleton plays a role in wrapping electrolyte and photo-thermal materials.
In the hydrogel electrolyte, the mass ratio of the high molecular polymer skeleton to the cross-linking agent is (0.5-2): 4, preferably 1: 4.
The cross-linking agent comprises N, N-Dimethylacrylamide (DMAA) and N, N-Methylene Bisacrylamide (MBAA), and the cross-linking agent and hydroxyl groups in the high-molecular polymer monomer are subjected to condensation reaction to generate a net structure, so that electrolyte ions can be rapidly transferred, and the ion conductivity can be improved.
When the crosslinking agent is a mixture of N, N-Dimethylacrylamide (DMAA) and N, N-methylenebisacrylamide, the mass ratio of N, N-Dimethylacrylamide (DMAA) to N, N-methylenebisacrylamide is 1: 3.
The metal salt solution includes a sodium acetate solution (NaAc), a potassium acetate solution (KAc), a sodium chloride solution (NaCl), and a potassium chloride solution (KCl).
In the hydrogel electrolyte, the concentration of the metal salt solution is saturated concentration, the saturated solution, namely the metal salt solid, is dissolved in the liquid until the saturated solution can not be dissolved, and the saturated metal salt solution can effectively reduce the freezing point of the hydrogel, so that the gel electrolyte has excellent conductivity at low temperature, and the cold-resistant characteristic is endowed to the gel electrolyte.
The hydrogel electrolyte exhibits a porous network structure.
The second purpose of the invention is to provide a preparation method of a cold-resistant solar-driven photothermal effect hydrogel electrolyte, which comprises the following steps:
(1) dissolving a high molecular polymer monomer and a cross-linking agent in water, mixing, and reacting to obtain a reaction solution with a high molecular polymer skeleton;
(2) adding a transition metal sulfide into the reaction solution to form a dispersion;
(3) then putting the dispersion into a mould for freeze drying to form hydrogel;
(4) and taking out the freeze-dried hydrogel and soaking the hydrogel in a metal salt solution.
In the step (1), the mass ratio of the high molecular polymer monomer to water is (0.5-2): 10, preferably 1: 10.
In the step (1), when the crosslinking agent is a mixture of N, N-Dimethylacrylamide (DMAA) and N, N-methylenebisacrylamide, the mass ratio of the N, N-dimethylacrylamide to water is 1:10, and the mass ratio of the N, N-methylenebisacrylamide to water is 3: 10.
In the step (1), during mixing, the temperature of water is 80-100 ℃, preferably 90 ℃, the high molecular polymer monomer can be dissolved in the water and react with the cross-linking agent at high temperature, and cannot be dissolved or react at room temperature.
In the step (2), the concentration of the transition metal sulfide in the dispersion is 0.2-1.0 mg/mL, preferably 0.8 mg/mL.
In the step (3), the temperature of freeze drying is-50 to-30 ℃, preferably-40 ℃, and the time of freeze drying is 2.5 to 3.5 hours, preferably 3 hours.
In the step (3), the mold is made of polytetrafluoroethylene, so that hydrogel can be conveniently removed subsequently, and the mold does not react with the hydrogel.
In the step (4), the volume ratio of the metal salt solution to the water taken in the step (1) is (40-60): 1, and preferably 50: 1.
In the step (4), the metal salt solution is soaked for 22-26 hours, preferably 24 hours.
The third purpose of the invention is to provide the application of the cold-resistant solar-driven photothermal effect hydrogel electrolyte in the super capacitor. The hydrogel electrolyte and the carbon fiber electrode are directly combined to form the supercapacitor for use.
Studies have shown that Transition Metal Disulfides (TMDs), such as molybdenum disulfide nanoplates and tungsten disulfide nanoplates, have been used as effective photothermal materials in the fields of power generators, wound antimicrobial or cancer therapy, water desalination or purification.
The invention discloses a hydrogel electrolyte with solar-driven heating capacity and cold resistance through the self-initiation effect of transition metal disulfides such as molybdenum disulfide nanosheets or tungsten disulfide nanosheets and the effect that a saturated metal salt solution can reduce the freezing point of hydrogel, and a novel double-photo-thermal micro supercapacitor with solar-assisted enhanced electrochemical performance is designed by utilizing the composite hydrogel electrolyte and a carbon fiber electrode. The hydrogel has the advantages of high energy utilization rate, low water vaporization energy requirement, strong physicochemical property adjustability and the like, can achieve the required size and shape by using a corresponding mould according to the requirement during gelation, has good expandability, can drive the photo-thermal material to absorb light energy and convert the solar energy into heat energy, and can work at the temperature of minus 30 ℃ because the hydrogel electrolyte also has cold resistance.
Drawings
FIG. 1 is an SEM electron micrograph of the cold-resistant solar-driven photothermal effect hydrogel electrolyte prepared in example 1;
FIG. 2 shows that the concentration of molybdenum disulfide nanosheet cold-resistant solar-driven photothermal effect hydrogel electrolyte is 1 w-cm2Comparing the temperature change of the soaked and non-soaked materials under infrared illumination;
FIG. 3 is a graph showing the specific capacity of a cold-resistant solar-driven photothermal effect hydrogel electrolyte as a function of current density under dark and sunlight conditions;
FIG. 4 is a graph showing the measurement of the charge and discharge curves of the cold-resistant solar-driven photothermal effect hydrogel electrolyte under different temperature conditions;
FIG. 5 is a plot of cyclic voltammograms of the supercapacitor made in example 6 under sunlight and dark conditions.
Detailed Description
The invention is described in detail below with reference to the figures and specific embodiments. The present embodiment is implemented on the premise of the technical solution of the present invention, and a detailed implementation manner and a specific operation process are given, but the scope of the present invention is not limited to the following embodiments.
In the following examples, unless otherwise specified, all of the conventional commercial starting materials and conventional processing techniques are used.
Example 1
A cold-resistant solar-driven photothermal effect hydrogel electrolyte comprises a solar-driven photothermal material, a high molecular polymer framework, a cross-linking agent and a metal salt solution, wherein the solar-driven photothermal material is a transition metal sulfide, specifically molybdenum disulfide, the high molecular polymer framework is prepared by polymerizing polyvinyl alcohol through two cross-linking agents of N, N-dimethylacrylamide and N, N-methylene bisacrylamide, and the metal salt is a KCl solution. The preparation steps are as follows:
1) 0.1g of N, N-Dimethylacrylamide (DMAA), 0.3g of N, N-Methylenebisacrylamide (MBAA) and 0.1g of polyvinyl alcohol were dissolved in 1mL of distilled water having a temperature of 90 ℃ with continuous stirring.
2) And then adding molybdenum disulfide nanosheets with the mass of 0.8mg into the solution to form a molybdenum disulfide nanosheet uniform dispersion.
3) Then adding the dispersion into a polytetrafluoroethylene mold for molding.
4) Then put into a freeze dryer to be freeze-dried for 3 hours at the temperature of minus 40 ℃.
5) And finally, soaking the hydrogel subjected to freeze drying in 50ml of saturated KCl solution for 24 hours at room temperature to obtain the cold-resistant solar-driven photothermal effect hydrogel electrolyte.
6) Fig. 1 is an SEM electron micrograph of the cold-resistant solar-driven photothermal effect hydrogel electrolyte, and it can be seen that the obtained hydrogel electrolyte exhibits a porous network structure, which improves the ion transfer rate and increases the conductivity of the gel electrolyte.
Example 2
A cold-resistant solar-driven photothermal effect hydrogel electrolyte comprises a solar-driven photothermal material, a high molecular polymer framework, a cross-linking agent and a metal salt solution, wherein the solar-driven photothermal material is a transition metal sulfide, specifically molybdenum disulfide, the high molecular polymer framework is prepared by polymerizing polyvinyl alcohol through two cross-linking agents of N, N-dimethylacrylamide and N, N-methylene bisacrylamide, and the metal salt is a NaAc solution. The preparation steps are as follows:
1) 0.1g of N, N-Dimethylacrylamide (DMAA), 0.3g of N, N-Methylenebisacrylamide (MBAA) and 0.1g of polyvinyl alcohol were dissolved in 1mL of distilled water having a temperature of 90 ℃ with continuous stirring.
2) Different masses of molybdenum disulfide nanoplates (0.2, 0.4, 0.6, 0.8, 1.0mg) were then added to the above solution to form uniform dispersions (0.2, 0.4, 0.6, 0.8, 1.0mg/mL) with different concentrations of molybdenum disulfide nanoplates.
3) And then adding the uniform dispersion of the molybdenum disulfide nanosheets with different concentrations into a polytetrafluoroethylene mold for molding.
4) Then putting the mixture into a freeze dryer for freeze drying for 3 hours at the temperature of minus 40 ℃ to obtain composite hydrogel containing molybdenum disulfide with different concentrations, and then putting the obtained hydrogel into a container with the concentration of 1 w.cm2The temperature measurement under infrared illumination is performed, and the result is shown in fig. 2, it can be seen that the temperature of the hydrogel gradually increases with the increase of the content of the molybdenum disulfide, which indicates that more photothermal effect occurs, and compared with comparative example 1, which indicates that the photothermal effect of the electrolyte can be greatly enhanced by the transition metal sulfide, and the temperature difference is larger with the increase of the content of the transition metal sulfide, which indicates that the content of the transition metal sulfide is a key factor affecting the performance of the electrolyte.
5) Finally, soaking the polyvinyl alcohol hydrogel in 50ml of saturated NaAc solution for 24 hours at room temperature to obtain the polyvinyl alcohol hydrogelFinal cold-resistant solar-driven photothermal hydrogel electrolyte, placing the obtained electrolyte in a volume of 1w cm2The temperature measurement under infrared illumination is carried out, the result is shown in fig. 2, the temperature of the electrolyte is gradually increased along with the increase of the content of the molybdenum disulfide, which indicates that more photothermal effect occurs, and compared with comparative example 1, the photothermal effect of the electrolyte can be greatly enhanced by the transition metal sulfide, and the temperature difference is larger along with the increase of the content of the transition metal sulfide, which indicates that the content of the transition metal sulfide is a key factor influencing the performance of the electrolyte.
FIG. 2 shows that the cold-resistant solar-driven photothermal effect hydrogel electrolyte of molybdenum disulfide nanosheets with different concentrations is 1 w-cm2Comparison of the temperature changes of the immersion and non-immersion treatments under infrared illumination shows that the photothermal effect of the electrolyte can be greatly enhanced by immersion. Compared with the non-soaked hydrogel, ions enter the electrolyte after soaking, water in the original hydrogel electrolyte comes out of the electrolyte, and the water volume of the hydrogel electrolyte is reduced along with the loss of water. The hydrogel after soaking shows more prominent photothermal conversion capability, and the enhancement of the photothermal capability of the hydrogel can be attributed to the reduction of the water content of the hydrogel electrolyte and the reduction of the distance between the molybdenum disulfide nanosheets.
Example 3
A cold-resistant solar-driven photothermal effect hydrogel electrolyte comprises a solar-driven photothermal material, a high molecular polymer framework, a cross-linking agent and a metal salt solution, wherein the solar-driven photothermal material is a transition metal sulfide, specifically molybdenum disulfide, the high molecular polymer framework is prepared by polymerizing polyvinyl alcohol through two cross-linking agents of N, N-dimethylacrylamide and N, N-methylene bisacrylamide, and the metal salt is a NaAc solution. The preparation steps are as follows:
1) 0.1g of N, N-Dimethylacrylamide (DMAA), 0.3g of N, N-Methylenebisacrylamide (MBAA) and 0.1g of polyvinyl alcohol were dissolved in 1mL of distilled water having a temperature of 90 ℃ with continuous stirring.
2) And then adding molybdenum disulfide nanosheets with the mass of 0.8mg into the solution to form a molybdenum disulfide nanosheet uniform dispersion.
3) Then adding the dispersion into a polytetrafluoroethylene mold for molding.
4) And then putting the mixture into a freeze dryer to be frozen and dried for 3 hours at the temperature of minus 40 ℃ to obtain the composite hydrogel containing the molybdenum disulfide.
5) And finally, soaking the polyvinyl alcohol hydrogel in 50ml of saturated NaAc solution for 24 hours at room temperature to obtain the final cold-resistant solar-driven photothermal effect hydrogel electrolyte.
6) The obtained hydrogel electrolyte and a commercially available carbon fiber electrode are combined into a flexible supercapacitor, and the flexible supercapacitor is used in the dark and in the sunlight (the intensity is 1W/cm)2) The change of the specific capacity of the cold-resistant solar-driven thermal effect hydrogel electrolyte with the current density was measured under the conditions, as shown in fig. 3. As can be seen, under the dark condition, the specific capacity of the super capacitor is lower, and at the beginning of the experiment, the specific capacity is 24mF/cm2About, with the increase of current density, the current finally decays to 20mF/cm2Left and right. Under the irradiation of sunlight, the specific capacity of the super capacitor is higher, and in the initial experiment, the specific capacity is 42.5mF/cm2About, with the increase of current density, the current finally decays to 26mF/cm2Left and right. It is shown that the electrolyte prepared by the invention can be driven by solar energy.
Example 4
A cold-resistant solar-driven photothermal effect hydrogel electrolyte comprises a solar-driven photothermal material, a high molecular polymer framework, a cross-linking agent and a metal salt solution, wherein the solar-driven photothermal material is a transition metal sulfide, specifically molybdenum disulfide, the high molecular polymer framework is prepared by polymerizing polyvinyl alcohol through two cross-linking agents of N, N-dimethylacrylamide and N, N-methylene bisacrylamide, and the metal salt is a NaAc solution. The preparation steps are as follows:
1) 0.1g of N, N-Dimethylacrylamide (DMAA), 0.3g of N, N-Methylenebisacrylamide (MBAA) and 0.1g of polyvinyl alcohol were dissolved in 1mL of distilled water having a temperature of 90 ℃ with continuous stirring.
2) And then adding molybdenum disulfide nanosheets with the mass of 0.8mg into the solution to form a molybdenum disulfide nanosheet uniform dispersion.
3) Then adding the dispersion into a polytetrafluoroethylene mold for molding.
4) And then putting the mixture into a freeze dryer to be frozen and dried for 3 hours at the temperature of minus 40 ℃ to obtain the composite hydrogel containing the molybdenum disulfide.
5) And finally, soaking the polyvinyl alcohol hydrogel in 50ml of saturated NaAc solution for 24 hours at room temperature to obtain the final cold-resistant solar-driven photothermal effect hydrogel electrolyte.
6) The obtained gel electrolyte and the carbon fiber electrode are combined into a flexible supercapacitor, and the charge-discharge curve change of the supercapacitor is measured under different temperature conditions, as shown in fig. 4.
As can be seen from FIG. 4, the shapes of the charging and discharging curves at-30 deg.C, -20 deg.C, 0 deg.C and 20 deg.C are relatively consistent, which shows that the super capacitor made of the electrolyte prepared by the invention can be charged and discharged normally at low temperature, and shows that the electrolyte has cold-resistant property.
Comparative example 1
1) 0.1g of N, N-Dimethylacrylamide (DMAA), 0.3g of N, N-Methylenebisacrylamide (MBAA) and 0.1g of polyvinyl alcohol were dissolved in 1mL of distilled water having a temperature of 90 ℃ with continuous stirring.
2) Then adding the solution into a polytetrafluoroethylene mold for molding.
3) Then freeze-drying in a freeze-drying machine at-40 deg.C for 3 hr to obtain composite hydrogel, and placing the hydrogel in a container of 1 w.cm2Temperature measurements were made under infrared illumination and the results are shown in figure 2.
4) Finally, soaking the polyvinyl alcohol hydrogel in 50ml of saturated NaAc solution for 24 hours at room temperature to obtain the final cold-resistant solar-driven photothermal effect hydrogel electrolyte, and placing the obtained electrolyte in a 1 w-cm2Temperature measurements were made under infrared illumination and the results are shown in figure 2.
Example 5
A cold-resistant solar-driven photothermal effect hydrogel electrolyte comprises a solar-driven photothermal material, a high molecular polymer framework, a cross-linking agent and a metal salt solution, wherein the solar-driven photothermal material is a transition metal sulfide, specifically tungsten disulfide, the high molecular polymer framework is agarose and is obtained by polymerizing two cross-linking agents of N, N-dimethylacrylamide and N, N-methylene bisacrylamide, and the metal salt is a NaAc solution. The preparation steps are as follows:
1) 0.1g of N, N-Dimethylacrylamide (DMAA), 0.3g of N, N-Methylenebisacrylamide (MBAA) and 0.1g of agarose were dissolved in 1mL of distilled water having a temperature of 90 ℃ with continuous stirring.
2) And then adding tungsten disulfide nanosheets with the mass of 0.8mg into the solution to form the tungsten disulfide nanosheet uniform dispersion.
3) Then adding the dispersion into a polytetrafluoroethylene mold for molding.
4) And then putting the hydrogel into a freeze dryer to be frozen and dried for 3 hours at the temperature of minus 40 ℃ to obtain the composite hydrogel containing the tungsten disulfide.
5) And finally, soaking the agarose hydrogel in 50ml of saturated NaAc solution for 24 hours at room temperature to obtain the final cold-resistant solar-driven photothermal effect hydrogel electrolyte.
6) And combining the obtained hydrogel electrolyte with a commercially available carbon fiber electrode to form the flexible supercapacitor.
Example 6
A cold-resistant solar-driven photothermal effect hydrogel electrolyte comprises a solar-driven photothermal material, a high molecular polymer framework, a cross-linking agent and a metal salt solution, wherein the solar-driven photothermal material is a transition metal sulfide, specifically tungsten disulfide, the high molecular polymer framework is sodium alginate which is obtained by polymerizing two cross-linking agents of N, N-dimethylacrylamide and N, N-methylene bisacrylamide, and the metal salt is a NaCl solution. The preparation steps are as follows:
1) 0.1g of N, N-Dimethylacrylamide (DMAA), 0.3g of N, N-Methylenebisacrylamide (MBAA) and 0.1g of sodium alginate were dissolved in 1mL of distilled water having a temperature of 90 ℃ with continuous stirring.
2) And then adding tungsten disulfide nanosheets with the mass of 0.8mg into the solution to form the tungsten disulfide nanosheet uniform dispersion.
3) Then adding the dispersion into a polytetrafluoroethylene mold for molding.
4) And then putting the hydrogel into a freeze dryer to be frozen and dried for 3 hours at the temperature of minus 40 ℃ to obtain the composite hydrogel containing the tungsten disulfide.
5) And finally, soaking the sodium alginate hydrogel in 50ml of saturated NaCl solution for 24 hours at room temperature to obtain the final cold-resistant solar-driven photothermal effect hydrogel electrolyte.
6) The obtained hydrogel electrolyte and a commercially available carbon fiber electrode were combined into a flexible supercapacitor, and the change in voltammetry of the resulting supercapacitor was measured under light and dark conditions, as shown in fig. 5.
As can be seen from fig. 5, the cyclic voltammetry curves under sunlight and dark conditions are relatively consistent and have a quasi-rectangular shape, which illustrates that the super capacitor to which the hydrogel electrolyte prepared by the present invention is applied has double layer capacitance characteristics; meanwhile, the area enclosed by the curve under the sunlight condition is larger than that under the dark condition, which shows that the prepared hydrogel electrolyte has a light driving effect, and the specific capacitance of the super capacitor is greatly improved under the illumination condition.
Example 7
A cold-resistant solar-driven photothermal effect hydrogel electrolyte comprises a solar-driven photothermal material, a high molecular polymer framework, a cross-linking agent and a metal salt solution, wherein the solar-driven photothermal material is a transition metal sulfide, specifically molybdenum disulfide, the high molecular polymer framework is agarose and is obtained by polymerizing two cross-linking agents of N, N-dimethylacrylamide and N, N-methylene bisacrylamide, and the metal salt is a KAc solution. The preparation steps are as follows:
1) 0.1g of N, N-Dimethylacrylamide (DMAA), 0.3g of N, N-Methylenebisacrylamide (MBAA) and 0.1g of agarose were dissolved in 1mL of distilled water having a temperature of 90 ℃ with continuous stirring.
2) And then adding molybdenum disulfide nanosheets with the mass of 0.8mg into the solution to form a molybdenum disulfide nanosheet uniform dispersion.
3) Then adding the dispersion into a polytetrafluoroethylene mold for molding.
4) And then putting the mixture into a freeze dryer to be frozen and dried for 3 hours at the temperature of minus 40 ℃ to obtain the composite hydrogel containing the molybdenum disulfide.
5) Finally, the agarose hydrogel was soaked in 50ml of saturated KAc solution for 24 hours at room temperature to obtain the final cold-resistant solar-driven photothermal effect hydrogel electrolyte.
6) And combining the obtained gel electrolyte with a commercially available carbon fiber electrode to form the flexible supercapacitor.
Example 8
The cold-resistant solar-driven photothermal effect hydrogel electrolyte comprises a solar-driven photothermal material, a high molecular polymer framework, a cross-linking agent and a metal salt solution, wherein the solar-driven photothermal material is a transition metal sulfide, specifically molybdenum disulfide, the high molecular polymer framework is agarose and is obtained by polymerizing two cross-linking agents of N, N-dimethylacrylamide and N, N-methylene bisacrylamide, and the metal salt is a NaCl solution. The preparation steps are as follows:
1) 0.1g of N, N-Dimethylacrylamide (DMAA), 0.3g of N, N-Methylenebisacrylamide (MBAA) and 0.05g of agarose were dissolved in 1mL of distilled water having a temperature of 80 ℃ with continuous stirring.
2) And then adding molybdenum disulfide nanosheets with the mass of 0.2mg into the solution to form a molybdenum disulfide nanosheet uniform dispersion.
3) Then adding the dispersion into a polytetrafluoroethylene mold for molding.
4) And then putting the mixture into a freeze dryer to be frozen and dried for 2.5 hours at the temperature of minus 50 ℃ to obtain the composite hydrogel containing the molybdenum disulfide.
5) And finally, soaking the agarose hydrogel in 40ml of saturated NaCl solution for 22 hours at room temperature to obtain the final cold-resistant solar-driven photothermal effect hydrogel electrolyte.
6) And combining the obtained gel electrolyte with a commercially available carbon fiber electrode to form the flexible supercapacitor.
Example 9
A cold-resistant solar-driven photothermal effect hydrogel electrolyte comprises a solar-driven photothermal material, a high molecular polymer framework, a cross-linking agent and a metal salt solution, wherein the solar-driven photothermal material is a transition metal sulfide, specifically molybdenum disulfide, the high molecular polymer framework is agarose and is obtained by polymerizing two cross-linking agents of N, N-dimethylacrylamide and N, N-methylene bisacrylamide, and the metal salt is a KCl solution. The preparation steps are as follows:
1) 0.1g of N, N-Dimethylacrylamide (DMAA), 0.3g of N, N-Methylenebisacrylamide (MBAA) and 0.2g of agarose were dissolved in 1mL of distilled water having a temperature of 80 ℃ with continuous stirring.
2) And then adding molybdenum disulfide nanosheets with the mass of 0.2mg into the solution to form a molybdenum disulfide nanosheet uniform dispersion.
3) Then adding the dispersion into a polytetrafluoroethylene mold for molding.
4) And then putting the hydrogel into a freeze dryer to be frozen and dried for 3.5 hours at the temperature of minus 30 ℃ to obtain the composite hydrogel containing the molybdenum disulfide.
5) And finally, soaking the agarose hydrogel in 60ml of saturated KCl solution for 26 hours at room temperature to obtain the final cold-resistant solar-driven photothermal effect hydrogel electrolyte.
6) And combining the obtained gel electrolyte with a commercially available carbon fiber electrode to form the flexible supercapacitor.
The embodiments described above are described to facilitate an understanding and use of the invention by those skilled in the art. It will be readily apparent to those skilled in the art that various modifications to these embodiments may be made, and the generic principles described herein may be applied to other embodiments without the use of the inventive faculty. Therefore, the present invention is not limited to the above embodiments, and those skilled in the art should make improvements and modifications within the scope of the present invention based on the disclosure of the present invention.
Claims (10)
1. The utility model provides a cold-resistant solar drive light and heat effect aquogel electrolyte which characterized in that, aquogel electrolyte includes solar drive light and heat material, macromolecular polymer skeleton, cross-linking agent and metal salt solution, solar drive light and heat material is transition metal sulphide.
2. The cold-resistant solar-driven photothermal effect hydrogel electrolyte of claim 1 wherein said transition metal sulfide comprises molybdenum disulfide and tungsten disulfide.
3. The cold-resistant solar-driven photothermal effect hydrogel electrolyte according to claim 1, wherein the constituent monomers of the high molecular polymer skeleton comprise one or more of polyvinyl alcohol, agarose or sodium alginate.
4. The cold-resistant solar-driven photothermal effect hydrogel electrolyte according to claim 1, wherein the mass ratio of the high molecular polymer backbone to the cross-linking agent in the hydrogel electrolyte is 1: 4.
5. The cold-resistant solar-driven photothermal effect hydrogel electrolyte of claim 1 wherein said cross-linking agent comprises N, N-dimethylacrylamide and N, N-methylenebisacrylamide.
6. The cold-resistant solar-driven photothermal effect hydrogel electrolyte according to claim 5, wherein when the crosslinking agent is a mixture of N, N-dimethylacrylamide and N, N-methylenebisacrylamide, the mass ratio of N, N-dimethylacrylamide to N, N-methylenebisacrylamide is 1: 3.
7. The cold-resistant solar-driven photothermal effect hydrogel electrolyte of claim 1 wherein said metal salt solution comprises sodium acetate solution, potassium acetate solution, sodium chloride solution and potassium chloride solution.
8. The cold-resistant solar-driven photothermal effect hydrogel electrolyte according to claim 1, wherein the concentration of said metal salt solution in the hydrogel electrolyte is a saturation concentration.
9. A method for preparing the cold-resistant solar-driven photothermal effect hydrogel electrolyte as claimed in any one of claims 1 to 8, wherein the method comprises the following steps:
(1) dissolving a high molecular polymer monomer and a cross-linking agent in water, mixing, and reacting to obtain a reaction solution with a high molecular polymer skeleton;
(2) adding a transition metal sulfide into the reaction solution to form a dispersion;
(3) then putting the dispersion into a mould for freeze drying to form hydrogel;
(4) and taking out the freeze-dried hydrogel and soaking the hydrogel in a metal salt solution.
10. Use of the cold-resistant solar-driven photothermal effect hydrogel electrolyte of any one of claims 1-8 in a supercapacitor.
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