CN114256000A - Assembly method of asymmetric supercapacitor based on PVA-PMA-SA-TA self-healing gel - Google Patents
Assembly method of asymmetric supercapacitor based on PVA-PMA-SA-TA self-healing gel Download PDFInfo
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- 239000000017 hydrogel Substances 0.000 claims description 64
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium peroxydisulfate Substances [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 34
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 34
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 claims description 28
- VAZSKTXWXKYQJF-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)OOS([O-])=O VAZSKTXWXKYQJF-UHFFFAOYSA-N 0.000 claims description 27
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- LRBQNJMCXXYXIU-PPKXGCFTSA-N Penta-digallate-beta-D-glucose Natural products OC1=C(O)C(O)=CC(C(=O)OC=2C(=C(O)C=C(C=2)C(=O)OC[C@@H]2[C@H]([C@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)O2)OC(=O)C=2C=C(OC(=O)C=3C=C(O)C(O)=C(O)C=3)C(O)=C(O)C=2)O)=C1 LRBQNJMCXXYXIU-PPKXGCFTSA-N 0.000 claims description 7
- LRBQNJMCXXYXIU-NRMVVENXSA-N tannic acid Chemical compound OC1=C(O)C(O)=CC(C(=O)OC=2C(=C(O)C=C(C=2)C(=O)OC[C@@H]2[C@H]([C@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)O2)OC(=O)C=2C=C(OC(=O)C=3C=C(O)C(O)=C(O)C=3)C(O)=C(O)C=2)O)=C1 LRBQNJMCXXYXIU-NRMVVENXSA-N 0.000 claims description 7
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- 238000002360 preparation method Methods 0.000 claims description 6
- IXPNQXFRVYWDDI-UHFFFAOYSA-N 1-methyl-2,4-dioxo-1,3-diazinane-5-carboximidamide Chemical compound CN1CC(C(N)=N)C(=O)NC1=O IXPNQXFRVYWDDI-UHFFFAOYSA-N 0.000 claims description 5
- 229920002845 Poly(methacrylic acid) Polymers 0.000 claims description 5
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- LCPVQAHEFVXVKT-UHFFFAOYSA-N 2-(2,4-difluorophenoxy)pyridin-3-amine Chemical compound NC1=CC=CN=C1OC1=CC=C(F)C=C1F LCPVQAHEFVXVKT-UHFFFAOYSA-N 0.000 claims description 2
- 238000004090 dissolution Methods 0.000 claims description 2
- CWQXQMHSOZUFJS-UHFFFAOYSA-N molybdenum disulfide Chemical compound S=[Mo]=S CWQXQMHSOZUFJS-UHFFFAOYSA-N 0.000 claims description 2
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- 238000002791 soaking Methods 0.000 claims description 2
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Substances [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 claims description 2
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/54—Electrolytes
- H01G11/56—Solid electrolytes, e.g. gels; Additives therein
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/84—Processes for the manufacture of hybrid or EDL capacitors, or components thereof
- H01G11/86—Processes for the manufacture of hybrid or EDL capacitors, or components thereof specially adapted for electrodes
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- Engineering & Computer Science (AREA)
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- Microelectronics & Electronic Packaging (AREA)
- Chemical & Material Sciences (AREA)
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- Electrochemistry (AREA)
- Manufacturing & Machinery (AREA)
- Electric Double-Layer Capacitors Or The Like (AREA)
Abstract
The invention discloses an assembling method of an asymmetric supercapacitor based on PVA-PMA-SA-TA self-healing gel; according to the invention, by utilizing the self-healing performance of the electrolyte, the two integrated super capacitors with different electrode materials are cut along the electrolyte, and then the two super capacitors with different electrode materials can be assembled into a new asymmetric super capacitor through the self-healing performance of the electrolyte. The invention simultaneously solves the problems that the voltage window of the integrally prepared super capacitor is smaller and the super capacitor assembled by a laminating method is easy to deform. The method has the advantages of simplicity, high efficiency and high cost performance. The material prepared by the method has the characteristics of wider working voltage, higher energy density and power density, foldability, self-healing and the like.
Description
Technical Field
The invention belongs to the field of super-capacitor new material energy storage, and particularly relates to an assembling method of an asymmetric capacitor based on self-healing gel.
Background
In recent years, stretchable and curable electronic products have received much attention due to their excellent flexibility, high reliability and stable resistance to deformation. In order to better meet the functional requirements of the above electronic devices, the development of corresponding energy storage devices with stretchable and repairable properties is an urgent need for researchers. Currently, self-repairing flexible supercapacitors are widely studied for their long cycle stability, fast charge and discharge, high power density, and self-recovery capability after continuous mechanical deformation or physical damage.
Conventional flexible supercapacitors typically have a layered, multi-layer structure consisting of a polymer electrolyte sandwiched between two stacked electrodes. Devices of this structure are susceptible to weakening of the layer-to-layer bonds upon multiple bending, thereby allowing layer-to-layer slippage and irreversible delamination of the entire device. Such structural instability may result in degradation of device performance and even functional failure in actual use. The supercapacitor prepared by the integrated method is characterized in that an electrode material is polymerized onto an electrolyte material, so that the defects of the supercapacitor prepared by the traditional method can be overcome. However, in the process of polymerizing the electrode material, the polymerization area cannot be controlled artificially, so that the integrated preparation method can only prepare symmetrical supercapacitors. This, in turn, limits the range of operating voltages of the supercapacitor, resulting in a reduction in the energy density of the device.
The preparation of the asymmetric super capacitor is one of the ways for improving the energy density of the super capacitor. The asymmetric super capacitor uses two different materials as electrodes, and uses the material with relatively positive potential as anode and the other material as cathode. This can result in an increase in the voltage window of the supercapacitor, and thus an increase in the energy density of the supercapacitor.
At present, in order to solve the problem that a device is easy to break in the using process, a super capacitor with self-healing performance is a research hotspot and a research difficulty at present. The self-healing performance of the super capacitor is realized by mainly depending on the self-healing performance of electrolyte, and PVA (polyvinyl alcohol), borax, TA (tannic acid) and the like have good self-healing performance in various self-healing materials.
The self-healing performance of the electrolyte is utilized, the two integrated super capacitors with different electrode materials are cut along the electrolyte, and then the two super capacitors with different electrode materials can be assembled into a new asymmetric super capacitor through the self-healing performance of the electrolyte. Meanwhile, the problems that the voltage window of the integrally prepared super capacitor is small and the super capacitor assembled by a stacking method is easy to deform are solved.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides the MoS with self-healing property and high flexibility by utilizing the self-healing capability of the PVA-PMA-SA-TA gel electrolyte2-PPy// PVA-PMA-SA-TA// PPy asymmetric supercapacitor assembly method.
A method for assembling an asymmetric supercapacitor based on PVA-PMA-SA-TA self-healing gel is characterized by comprising the following steps:
(1) dissolving polyvinyl alcohol (PVA) into deionized water, and stirring at 95 ℃ for 2 hours to obtain a clear and transparent solution; wherein the mass ratio of PVA to deionized water is 1: 10;
(2) adding sodium alginate SA and methacrylic acid MA into the solution in the step one (1), and stirring for 3 hours; wherein the mass ratio of SA to MA is 1:10, and the mass ratio of MA to PVA is (1.5-2.5): 1;
(3) adding sodium persulfate APS into the solution prepared in the step one (2), wherein the mass ratio of APS to MA is 1:1, and reacting the solution at 60 ℃ for 2 hours to polymerize methacrylic acid MA into polymethacrylic acid PMA; taking out after reaction, naturally cooling, and freeze-drying by a freeze dryer;
(4) soaking the freeze-dried gel in 5-15 wt.% of tannic acid at room temperature for 24-48 hours to obtain PVA-PMA-SA-TA hydrogel;
step two: MoS2-PPy//PVA-PMA-SA-TA//MoS2Preparation of-PPy integrated symmetrical super capacitor
(1) Molybdenum disulfide MoS2Adding the powder and pyrrole Py into 0.5mol/L sulfuric acid solution, MoS2The molar ratio of Py to Py was 1 (1-4), the molar ratio of Py to sulfuric acid was 1:1.25, and ultrasonic dissolution was performed for 30 minutes.
(2) Cutting the self-healing PVA-PMA-SA-TA hydrogel into pieces with the length, width and height of (2-10): (2-10): placing a cube of 0.5cm into the solution obtained in the step two (1), and standing for 20 minutes;
(3) dissolving ammonium persulfate into a 0.5mol/L sulfuric acid solution, wherein the molar ratio of the ammonium persulfate to pyrrole is 1:1, the molar ratio of the ammonium persulfate to sulfuric acid is 1:1.25, and dissolving for 30 minutes by using ultrasonic;
(4) taking out the hydrogel in the step two (2), putting the hydrogel into the solution in the step two (3) for polymerization reaction, and placing the solution in an environment with the temperature of 0-4 ℃;
(5) after 4 hours of in-situ polymerization, the electrode MoS2Sufficiently growing PPy on the electrolyte, taking out the electrolyte, cleaning surface impurities with deionized water and ethanol, drying, cutting the peripheral edge to expose the interface between the electrolyte and the electrode, and layering to obtain MoS2-PPy//PVA-PMA-SA-TA//MoS2-PPy integrated supercapacitors.
Step three: preparation of PPy// PVA-PMA-SA-TA// PPy integrated supercapacitor
(1) Adding pyrrole Py into 0.5mol/L sulfuric acid solution, wherein the molar ratio of Py to sulfuric acid is 1:1.25, and dissolving for 30 minutes by using ultrasonic;
(2) cutting the self-healing PVA-PMA-SA-TA hydrogel into pieces with the length, width and height of (2-10): (2-10): placing a cube of 0.5cm into the solution obtained in the step three (1), and standing for 20 minutes;
(3) dissolving ammonium persulfate into a 0.5mol/L sulfuric acid solution, wherein the molar ratio of the ammonium persulfate to pyrrole is 1:1, the molar ratio of the ammonium persulfate to sulfuric acid is 1:1.25, and dissolving for 30 minutes by using ultrasonic;
(4) and (3) taking out the hydrogel in the step three (2), putting the hydrogel into the solution in the step three (3) for polymerization reaction, and placing the solution in an environment of 0-4 ℃.
(5) After 4 hours of in-situ polymerization reaction, the PPy electrode fully grows on the electrolyte, the electrolyte is taken out and then surface impurities are washed by deionized water and ethanol, after drying, the peripheral edge is cut off, and the interface of the electrolyte and the electrode is layered, thus obtaining the PPy/PVA-PMA-SA-TA/PPy integrated supercapacitor.
The method for preparing the all-solid-state asymmetric supercapacitor comprises the following steps:
mixing MoS2-PPy//PVA-PMA-SA-TA//MoS2The PPy supercapacitor was cut along the electrolyte to obtain two symmetrical and only one side polymerized MoS as shown in FIG. 12PVA-PMA-SA-TA hydrogel of PPy.
The PPy// PVA-PMA-SA-TA// PPy supercapacitor was cut along the electrolyte to give two symmetrical PVA-PMA-SA-TA hydrogels with PPy polymerized on only one side as shown in FIG. 1. Taking out half of each of two symmetrical hydrogels, bonding the hydrogel surfaces together, standing for 1-3 hours, and obtaining the electrolyte PVA-PMA-SA-TA by the self-healing performance of the PVA-PMA-SA-TA hydrogel and the anode MoS2-PPy, the cathode being an asymmetric supercapacitor of PPy.
The invention has the beneficial effects that: the method has the advantages of simplicity, high efficiency and high cost performance. The material prepared by the method has the characteristics of wider working voltage, higher energy density and power density, foldability, self-healing and the like.
Drawings
FIG. 1. the assembly process of the integrated asymmetric supercapacitor.
Detailed Description
For a better understanding of the present invention, reference is made to the following detailed description of the invention taken in conjunction with the accompanying drawings
As shown in FIG. 1, the assembly process of the integrated asymmetric supercapacitor comprises two steps, wherein MoS2the-PPy electrode 1 and the PVA-PMA-SA-TA electrolyte 2 form MoS2-PPy//PVA-PMA-SA-TA//MoS2The PPy super capacitor is formed by the PPy electrode 3 and the PVA-PMA-SA-TA electrolyte 2. Cutting two supercapacitors along the electrolyte to obtain two symmetrical PVA-PMA-SA-TA hydrogel with PPy polymerized on only one surfaceGlue and two symmetrical and only one side polymerized MoS2Taking half of each of two symmetrical parts of PVA-PMA-SA-TA hydrogel of PPy, bonding the hydrogel surfaces together, standing for 1-3 hours to obtain PVA-PMA-SA-TA as electrolyte and MoS as anode2-PPy, the cathode being an asymmetric supercapacitor of PPy.
The first embodiment is as follows:
1g of polyvinyl alcohol PVA was dissolved in 10mL of deionized water, and the solution was stirred at 95 ℃ for 2 hours to give a clear and transparent solution. 0.15g of sodium alginate SA and 1.5g of methacrylic acid MA were dissolved in the PVA solution, and the mixture was stirred for 3 hours. Slowly adding 1.5g of ammonium persulfate APS into the solution, and placing the solution at 60 ℃ for reacting for 2 hours to polymerize methacrylic acid MA into polymethacrylic acid PMA; taking out after reaction, naturally cooling, and freeze-drying with a freeze dryer. The freeze-dried gel was soaked in 5 wt.% tannic acid for 24 hours at room temperature. Thus obtaining the PVA-PMA-SA-TA hydrogel.
0.16g of MoS2And 0.275mL of pyrrole Py was added to 10mL of a 0.5mol/L sulfuric acid solution, and dissolved for 30 minutes using sonication. The PVA-PMA-SA-TA hydrogel was cut into a cube having a length, width and height of 2cm, 2cm and 0.5cm, and the cube was placed in the resulting solution and allowed to stand for 20 minutes. 0.912g of ammonium persulfate was dissolved in 10mL of a 0.5mol/L sulfuric acid solution, and dissolved for 30 minutes using sonication. Taking out the PVA-PMA-SA-TA hydrogel after standing, putting the PVA-PMA-SA-TA hydrogel into a sulfuric acid solution containing ammonium persulfate to carry out polymerization reaction, and putting the solution in an environment at 0 ℃. After 4 hours of in-situ polymerization, the electrode MoS2Sufficiently growing PPy on the electrolyte, taking out the electrolyte, cleaning surface impurities with deionized water and ethanol, drying, cutting the peripheral edge to expose the interface between the electrolyte and the electrode, and layering to obtain MoS2-PPy//PVA-PMA-SA-TA//MoS2-PPy integrated supercapacitors.
0.275mL of pyrrole Py was added to 10mL of a 0.5mol/L sulfuric acid solution, and dissolved for 30 minutes by sonication. The PVA-PMA-SA-TA hydrogel was cut into a cube having a length, width and height of 2cm, 2cm and 0.5cm, and the cube was placed in the resulting solution and allowed to stand for 20 minutes. 0.912g of ammonium persulfate was dissolved in 10mL of a 0.5mol/L sulfuric acid solution, and dissolved for 30 minutes using sonication. Taking out the PVA-PMA-SA-TA hydrogel after standing, putting the PVA-PMA-SA-TA hydrogel into a sulfuric acid solution containing ammonium persulfate to carry out polymerization reaction, and putting the solution in an environment at 0 ℃. After 4 hours of in-situ polymerization reaction, the PPy electrode fully grows on the electrolyte, the electrolyte is taken out and then surface impurities are washed by deionized water and ethanol, after drying, the peripheral edge is cut off, and the interface of the electrolyte and the electrode is layered, thus obtaining the PPy/PVA-PMA-SA-TA/PPy integrated supercapacitor.
Mixing MoS2-PPy//PVA-PMA-SA-TA//MoS2The PPy supercapacitor was cut along the electrolyte to obtain two symmetrical and only one side polymerized MoS as shown in FIG. 12PVA-PMA-SA-TA hydrogel of PPy.
The PPy// PVA-PMA-SA-TA// PPy supercapacitor was cut along the electrolyte to give two symmetrical PVA-PMA-SA-TA hydrogels with PPy polymerized on only one side as shown in FIG. 1. Taking out half of each of the two symmetrical hydrogels, bonding the hydrogel surfaces together, standing for 1 hour, and obtaining the electrolyte PVA-PMA-SA-TA by the self-healing performance of the PVA-PMA-SA-TA hydrogel and the anode MoS2-PPy, the cathode being an asymmetric supercapacitor of PPy.
The second embodiment is as follows:
1g of polyvinyl alcohol PVA was dissolved in 10mL of deionized water, and the solution was stirred at 95 ℃ for 2 hours to give a clear and transparent solution. 0.2g of sodium alginate SA and 2g of methacrylic acid MA were dissolved in the PVA solution and stirred for 3 hours. Slowly adding 2g of ammonium persulfate APS into the solution, and reacting the solution at 60 ℃ for 2 hours to polymerize methacrylic acid MA into polymethacrylic acid PMA; taking out after reaction, naturally cooling, and freeze-drying with a freeze dryer. The freeze-dried gel was soaked in 10 wt.% tannic acid for 36 hours at room temperature. Thus obtaining the PVA-PMA-SA-TA hydrogel.
0.32g of MoS2And 0.275mL of pyrrole Py was added to 10mL of a 0.5mol/L sulfuric acid solution, and dissolved for 30 minutes using sonication. Cutting PVA-PMA-SA-TA hydrogel into cubes with length, width and height of 6cm, 6cm and 0.5cm, adding into the obtained solution, and standing for 20And (3) minutes. 0.912g of ammonium persulfate was dissolved in 10mL of a 0.5mol/L sulfuric acid solution, and dissolved for 30 minutes using sonication. Taking out the PVA-PMA-SA-TA hydrogel after standing, putting the PVA-PMA-SA-TA hydrogel into a sulfuric acid solution containing ammonium persulfate to carry out polymerization reaction, and putting the solution in an environment at 2 ℃. After 4 hours of in-situ polymerization, the electrode MoS2Sufficiently growing PPy on the electrolyte, taking out the electrolyte, cleaning surface impurities with deionized water and ethanol, drying, cutting the peripheral edge to expose the interface between the electrolyte and the electrode, and layering to obtain MoS2-PPy//PVA-PMA-SA-TA//MoS2-PPy integrated supercapacitors.
0.275mL of pyrrole Py was added to 10mL of a 0.5mol/L sulfuric acid solution, and dissolved for 30 minutes by sonication. The PVA-PMA-SA-TA hydrogel was cut into a cube having a length, width and height of 6cm, 6cm and 0.5cm, and the cube was placed in the resulting solution and allowed to stand for 20 minutes. 0.912g of ammonium persulfate was dissolved in 10mL of a 0.5mol/L sulfuric acid solution, and dissolved for 30 minutes using sonication. Taking out the PVA-PMA-SA-TA hydrogel after standing, putting the PVA-PMA-SA-TA hydrogel into a sulfuric acid solution containing ammonium persulfate to carry out polymerization reaction, and putting the solution in an environment at 2 ℃. After 4 hours of in-situ polymerization reaction, the PPy electrode fully grows on the electrolyte, the electrolyte is taken out and then surface impurities are washed by deionized water and ethanol, after drying, the peripheral edge is cut off, and the interface of the electrolyte and the electrode is layered, thus obtaining the PPy/PVA-PMA-SA-TA/PPy integrated supercapacitor.
Mixing MoS2-PPy//PVA-PMA-SA-TA//MoS2The PPy supercapacitor was cut along the electrolyte to obtain two symmetrical and only one side polymerized MoS as shown in FIG. 12PVA-PMA-SA-TA hydrogel of PPy.
The PPy// PVA-PMA-SA-TA// PPy supercapacitor was cut along the electrolyte to give two symmetrical PVA-PMA-SA-TA hydrogels with PPy polymerized on only one side as shown in FIG. 1. Taking out half of each of the two symmetrical hydrogels, bonding the hydrogel surfaces together, standing for 2 hours, and obtaining the electrolyte PVA-PMA-SA-TA by the self-healing performance of the PVA-PMA-SA-TA hydrogel and the anode MoS2-PPy, the cathode being an asymmetric supercapacitor of PPy.
The third concrete implementation mode:
1g of polyvinyl alcohol PVA was dissolved in 10mL of deionized water, and the solution was stirred at 95 ℃ for 2 hours to give a clear and transparent solution. 0.25g of sodium alginate SA and 2.5g of methacrylic acid MA were dissolved in the PVA solution, and the mixture was stirred for 3 hours. Slowly adding 2.5g of ammonium persulfate APS into the solution, and placing the solution at 60 ℃ for reacting for 2 hours to polymerize methacrylic acid MA into polymethacrylic acid PMA; taking out after reaction, naturally cooling, and freeze-drying with a freeze dryer. The freeze-dried gel was soaked in 15 wt.% tannic acid for 48 hours at room temperature. Thus obtaining the PVA-PMA-SA-TA hydrogel.
0.64g of MoS2And 0.275mL of pyrrole Py was added to 10mL of a 0.5mol/L sulfuric acid solution, and dissolved for 30 minutes using sonication. The PVA-PMA-SA-TA hydrogel was cut into a cube having a length, width and height of 10cm, 10cm and 0.5cm, and the cube was placed in the resulting solution and allowed to stand for 20 minutes. 0.912g of ammonium persulfate was dissolved in 10mL of a 0.5mol/L sulfuric acid solution, and dissolved for 30 minutes using sonication. Taking out the PVA-PMA-SA-TA hydrogel after standing, putting the PVA-PMA-SA-TA hydrogel into a sulfuric acid solution containing ammonium persulfate to carry out polymerization reaction, and putting the solution in an environment at 4 ℃. After 4 hours of in-situ polymerization, the electrode MoS2Sufficiently growing PPy on the electrolyte, taking out the electrolyte, cleaning surface impurities with deionized water and ethanol, drying, cutting the peripheral edge to expose the interface between the electrolyte and the electrode, and layering to obtain MoS2-PPy//PVA-PMA-SA-TA//MoS2-PPy integrated supercapacitors.
0.275mL of pyrrole Py was added to 10mL of a 0.5mol/L sulfuric acid solution, and dissolved for 30 minutes by sonication. The PVA-PMA-SA-TA hydrogel was cut into a cube having a length, width and height of 10cm, 10cm and 0.5cm, and the cube was placed in the resulting solution and allowed to stand for 20 minutes. 0.912g of ammonium persulfate was dissolved in 10mL of a 0.5mol/L sulfuric acid solution, and dissolved for 30 minutes using sonication. Taking out the PVA-PMA-SA-TA hydrogel after standing, putting the PVA-PMA-SA-TA hydrogel into a sulfuric acid solution containing ammonium persulfate to carry out polymerization reaction, and putting the solution in an environment at 4 ℃. After 4 hours of in-situ polymerization reaction, the PPy electrode fully grows on the electrolyte, the electrolyte is taken out and then surface impurities are washed by deionized water and ethanol, after drying, the peripheral edge is cut off, and the interface of the electrolyte and the electrode is layered, thus obtaining the PPy/PVA-PMA-SA-TA/PPy integrated supercapacitor.
Mixing MoS2-PPy//PVA-PMA-SA-TA//MoS2The PPy supercapacitor was cut along the electrolyte to obtain two symmetrical and only one side polymerized MoS as shown in FIG. 12PVA-PMA-SA-TA hydrogel of PPy.
The PPy// PVA-PMA-SA-TA// PPy supercapacitor was cut along the electrolyte to give two symmetrical PVA-PMA-SA-TA hydrogels with PPy polymerized on only one side as shown in FIG. 1. Taking out half of each of the two symmetrical hydrogels, bonding the hydrogel surfaces together, standing for 3 hours, and obtaining the electrolyte PVA-PMA-SA-TA by the self-healing performance of the PVA-PMA-SA-TA hydrogel and the anode MoS2-PPy, the cathode being an asymmetric supercapacitor of PPy.
Claims (3)
1. The assembling method of the asymmetric supercapacitor based on PVA-PMA-SA-TA self-healing gel is characterized by comprising the following steps: the method comprises the following steps:
the method comprises the following steps: preparing self-healing PVA-PMA-SA-TA hydrogel electrolyte;
(1) dissolving polyvinyl alcohol (PVA) into deionized water, and stirring at 95 ℃ for 2 hours to obtain a clear and transparent solution; wherein the mass ratio of PVA to deionized water is 1: 10;
(2) adding sodium alginate SA and methacrylic acid MA into the solution in the step one (1), and stirring for 3 hours; wherein the mass ratio of SA to MA is 1:10, and the mass ratio of MA to PVA is (1.5-2.5): 1;
(3) adding sodium persulfate APS into the solution prepared in the step one (2), wherein the mass ratio of APS to MA is 1:1, and reacting the solution at 60 ℃ for 2 hours to polymerize methacrylic acid MA into polymethacrylic acid PMA; taking out after reaction, naturally cooling, and freeze-drying by a freeze dryer;
(4) soaking the freeze-dried gel in 5-15 wt.% of tannic acid at room temperature for 24-48 hours to obtain PVA-PMA-SA-TA hydrogel;
step two：MoS2-PPy//PVA-PMA-SA-TA//MoS2-preparing a PPy integrated symmetric supercapacitor;
step three: preparation of PPy// PVA-PMA-SA-TA// PPy integrated supercapacitor
Step four: mixing MoS2-PPy//PVA-PMA-SA-TA//MoS2The PPy supercapacitor is cut along the electrolyte to obtain two symmetrical supercapacitors with only one side polymerized with MoS2-PVA-PMA-SA-TA hydrogel of PPy;
step five: cutting the PPy// PVA-PMA-SA-TA// PPy supercapacitor along the electrolyte to obtain two symmetrical PAA-SA-TA hydrogels with only one side polymerized with PPy;
step six: taking out half of each of two symmetrical hydrogels, bonding the hydrogel surfaces together, standing for 1-3 hours, and obtaining the electrolyte PVA-PMA-SA-TA by the self-healing performance of the PVA-PMA-SA-TA hydrogel and the anode MoS2-PPy, the cathode being an asymmetric supercapacitor of PPy.
2. The method for assembling an asymmetric supercapacitor based on a PVA-PMA-SA-TA self-healing gel according to claim 1, wherein:
the MoS2-PPy//PVA-PMA-SA-TA//MoS2-preparing a PPy integrated symmetric supercapacitor; the method specifically comprises the following steps:
(1) molybdenum disulfide MoS2Adding the powder and pyrrole Py into 0.5mol/L sulfuric acid solution, MoS2The molar ratio of Py to Py is 1 (1-4), the molar ratio of Py to sulfuric acid is 1:1.25, and ultrasonic dissolution is used for 30 minutes;
(2) cutting the self-healing PVA-PMA-SA-TA hydrogel into pieces with the length, width and height of (2-10): (2-10): placing a cube of 0.5cm into the solution obtained in the step two (1), and standing for 20 minutes;
(3) dissolving ammonium persulfate into a 0.5mol/L sulfuric acid solution, wherein the molar ratio of the ammonium persulfate to pyrrole is 1:1, the molar ratio of the ammonium persulfate to sulfuric acid is 1:1.25, and dissolving for 30 minutes by using ultrasonic;
(4) taking out the hydrogel in the step two (2), putting the hydrogel into the solution in the step two (3) for polymerization reaction, and placing the solution in an environment with the temperature of 0-4 ℃;
(5) after 4 hours of in-situ polymerization, the electrode MoS2Sufficiently growing PPy on the electrolyte, taking out the electrolyte, cleaning surface impurities with deionized water and ethanol, drying, cutting the peripheral edge to expose the interface between the electrolyte and the electrode, and layering to obtain MoS2-PPy//PVA-PMA-SA-TA//MoS2-PPy integrated supercapacitors.
3. The method for assembling an asymmetric supercapacitor based on a PVA-PMA-SA-TA self-healing gel according to claim 1, wherein: the preparation method of the PPy// PVA-PMA-SA-TA// PPy integrated supercapacitor specifically comprises the following steps:
(1) adding pyrrole Py into 0.5mol/L sulfuric acid solution, wherein the molar ratio of Py to sulfuric acid is 1:1.25, and dissolving for 30 minutes by using ultrasonic;
(2) cutting the self-healing PVA-PMA-SA-TA hydrogel into pieces with the length, width and height of (2-10): (2-10): placing a cube of 0.5cm into the solution obtained in the step three (1), and standing for 20 minutes;
(3) dissolving ammonium persulfate into a 0.5mol/L sulfuric acid solution, wherein the molar ratio of the ammonium persulfate to pyrrole is 1:1, the molar ratio of the ammonium persulfate to sulfuric acid is 1:1.25, and dissolving for 30 minutes by using ultrasonic;
(4) taking out the hydrogel in the step three (2), putting the hydrogel into the solution in the step three (3) for polymerization reaction, and placing the solution in an environment with the temperature of 0-4 ℃;
(5) after 4 hours of in-situ polymerization reaction, the PPy electrode fully grows on the electrolyte, the electrolyte is taken out and then surface impurities are washed by deionized water and ethanol, after drying, the peripheral edge is cut off, and the interface of the electrolyte and the electrode is layered, thus obtaining the PPy/PVA-PMA-SA-TA/PPy integrated supercapacitor.
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