CN114256000B - Method for assembling self-healing gel-based asymmetric supercapacitor based on PVA-PMA-SA-TA - Google Patents
Method for assembling self-healing gel-based asymmetric supercapacitor based on PVA-PMA-SA-TA Download PDFInfo
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- 238000000034 method Methods 0.000 title claims abstract description 24
- 239000003792 electrolyte Substances 0.000 claims abstract description 61
- 208000022133 pulmonary valve agenesis Diseases 0.000 claims description 86
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 68
- 239000000017 hydrogel Substances 0.000 claims description 66
- 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
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 20
- 238000006116 polymerization reaction Methods 0.000 claims description 20
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 19
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 19
- 239000008367 deionised water Substances 0.000 claims description 17
- 229910021641 deionized water Inorganic materials 0.000 claims description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 17
- 239000000499 gel Substances 0.000 claims description 11
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 10
- 238000004140 cleaning Methods 0.000 claims description 10
- 239000012535 impurity Substances 0.000 claims description 10
- 230000002093 peripheral effect Effects 0.000 claims description 10
- 238000011065 in-situ storage Methods 0.000 claims description 9
- 238000002360 preparation method Methods 0.000 claims description 9
- TUSDEZXZIZRFGC-UHFFFAOYSA-N 1-O-galloyl-3,6-(R)-HHDP-beta-D-glucose Natural products OC1C(O2)COC(=O)C3=CC(O)=C(O)C(O)=C3C3=C(O)C(O)=C(O)C=C3C(=O)OC1C(O)C2OC(=O)C1=CC(O)=C(O)C(O)=C1 TUSDEZXZIZRFGC-UHFFFAOYSA-N 0.000 claims description 8
- 239000001263 FEMA 3042 Substances 0.000 claims description 8
- 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 8
- 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 8
- 229940033123 tannic acid Drugs 0.000 claims description 8
- 235000015523 tannic acid Nutrition 0.000 claims description 8
- 229920002258 tannic acid Polymers 0.000 claims description 8
- 238000004108 freeze drying Methods 0.000 claims description 7
- 238000003756 stirring Methods 0.000 claims description 7
- 238000005520 cutting process 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
- 238000006243 chemical reaction Methods 0.000 claims description 5
- 238000001816 cooling Methods 0.000 claims description 5
- 238000001035 drying Methods 0.000 claims description 5
- 235000010413 sodium alginate Nutrition 0.000 claims description 5
- 229940005550 sodium alginate Drugs 0.000 claims description 5
- 239000000661 sodium alginate Substances 0.000 claims description 5
- 238000004090 dissolution Methods 0.000 claims description 4
- 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
- CWQXQMHSOZUFJS-UHFFFAOYSA-N molybdenum disulfide Chemical compound S=[Mo]=S CWQXQMHSOZUFJS-UHFFFAOYSA-N 0.000 claims description 2
- 229910052982 molybdenum disulfide Inorganic materials 0.000 claims description 2
- 229920003229 poly(methyl methacrylate) Polymers 0.000 claims description 2
- 239000004926 polymethyl methacrylate Substances 0.000 claims description 2
- 239000000843 powder Substances 0.000 claims description 2
- 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
- 238000005868 electrolysis reaction Methods 0.000 claims 1
- 239000003990 capacitor Substances 0.000 abstract description 17
- 239000000463 material Substances 0.000 abstract description 7
- 239000007772 electrode material Substances 0.000 abstract description 6
- 238000003475 lamination Methods 0.000 abstract description 2
- 230000005611 electricity Effects 0.000 abstract 1
- 238000002604 ultrasonography Methods 0.000 description 12
- 229920002845 Poly(methacrylic acid) Polymers 0.000 description 3
- 230000007547 defect Effects 0.000 description 2
- 238000004146 energy storage Methods 0.000 description 2
- 230000000379 polymerizing effect Effects 0.000 description 2
- 241001391944 Commicarpus scandens Species 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910021538 borax Inorganic materials 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 230000032798 delamination Effects 0.000 description 1
- 239000002001 electrolyte material Substances 0.000 description 1
- 239000011245 gel electrolyte Substances 0.000 description 1
- 230000002427 irreversible effect Effects 0.000 description 1
- 239000005518 polymer electrolyte Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 235000010339 sodium tetraborate Nutrition 0.000 description 1
- 239000004328 sodium tetraborate Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
Classifications
-
- 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
-
- 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
-
- 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)
- Power Engineering (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Manufacturing & Machinery (AREA)
- Electric Double-Layer Capacitors Or The Like (AREA)
Abstract
The invention discloses an assembly method of an asymmetric supercapacitor based on PVA-PMA-SA-TA self-healing gel; according to the invention, by utilizing the self-healing property of the electrolyte, two integrated super capacitors with different electrode materials are cut along the electrolyte, and then the super capacitors with different electrode materials are assembled into a new asymmetric super capacitor through the self-healing property of the electrolyte. The invention solves the problems of small voltage window of the integrally prepared super capacitor and easy deformation of super electricity assembled by a lamination method. 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 new material energy storage of super capacitors, and particularly relates to an assembly method of an asymmetric capacitor based on self-healing gel.
Background
In recent years, stretchable and healable electronic products have received attention because of their excellent flexibility, high reliability and stable resistance to deformation. In order to better meet the functional requirements of the above-mentioned electronic devices, the development of corresponding energy storage devices with tensile and repairable properties is an urgent need for researchers. Currently, self-repairing flexible supercapacitors have been widely studied for their long-cycle stability, rapid charge and discharge, high power density, and self-recovery capability after continuous mechanical deformation or physical damage.
Conventional flexible supercapacitors typically have a layered multilayer structure, consisting of a polymer electrolyte sandwiched between two stacked electrodes. Devices of this construction tend to weaken the layer-to-layer bond with multiple bends, allowing slippage and irreversible delamination between layers to occur throughout the device. Such structural instability can degrade device performance and even function failure in actual use. The supercapacitor prepared by the integrated method is prepared by polymerizing the electrode material onto the electrolyte material, so that the defects of the supercapacitor prepared by the traditional method can be avoided. However, in the process of polymerizing the electrode material, the polymerized region cannot be controlled manually, so that the integrated preparation method can only prepare the symmetrical supercapacitor. This limits the range of supercapacitor operating voltages, which reduces the energy density of the device.
The preparation of asymmetric supercapacitors is one way to increase the energy density of supercapacitors. The asymmetric super capacitor uses two different materials as electrodes, uses a material with relatively positive potential as an anode, and uses the other material as a cathode. This can increase the voltage window of the supercapacitor, thereby increasing the energy density of the supercapacitor.
Currently, in order to solve the problem that devices are easy to break in the using process, the super capacitor with the self-healing performance is a current research hotspot and a research difficulty. The self-healing performance of the super capacitor is realized by mainly relying 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.
By utilizing the self-healing property 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 property of the electrolyte. Meanwhile, the problems that the voltage window of the integrally prepared supercapacitor is smaller and the superelectricity assembled by a lamination method is easy to deform are solved.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides a MoS with self-healing property and high flexibility by utilizing the self-healing capability of PVA-PMA-SA-TA gel electrolyte 2 -PPy//PVA-PMA-SA-A method for assembling TA// PPy asymmetric super capacitor.
The method for assembling the self-healing gel-based asymmetric supercapacitor is characterized by comprising the following steps of:
(1) Dissolving polyvinyl alcohol PVA into deionized water, stirring for 2 hours at 95 ℃, and clarifying and transparentizing the 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, a step of;
(3) Adding sodium persulfate APS into the solution prepared in the step (2), wherein the mass ratio of the APS to the MA is 1:1, and reacting the solution at 60 ℃ for 2 hours to polymerize methacrylic acid MA into polymethyl methacrylate PMA; taking out after the reaction, naturally cooling, and freeze-drying by a freeze dryer;
(4) Soaking the gel after freeze drying in 5-15wt.% tannic acid for 24-48 hours at room temperature to obtain PVA-PMA-SA-TA hydrogel;
step two: moS (MoS) 2 -PPy//PVA-PMA-SA-TA//MoS 2 Preparation of PPy integrated symmetrical supercapacitor
(1) Molybdenum disulfide MoS 2 Adding the powder and pyrrole Py into 0.5mol/L sulfuric acid solution, moS 2 And Py is 1 (1-4), the mole ratio of Py to sulfuric acid is 1:1.25, and the dissolution is carried out for 30 minutes by using ultrasonic.
(2) Cutting self-healing PVA-PMA-SA-TA hydrogel into a hydrogel with 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 sulfuric acid solution with the concentration of 0.5mol/L, wherein the molar ratio of the ammonium persulfate to the pyrrole is 1:1, the molar ratio of the ammonium persulfate to the sulfuric acid is 1:1.25, and dissolving for 30 minutes by using ultrasonic;
(4) Taking out the hydrogel in the second step (2), putting the hydrogel into the solution in the second step (3) for polymerization reaction, and placing the solution in an environment of 0-4 ℃;
(5) Through 4 hoursIn-situ polymerization reaction, electrode MoS 2 PPy grows on the electrolyte fully, the electrolyte is taken out, deionized water and ethanol are used for cleaning surface impurities, and after drying, the peripheral edge is cut off, the interface layering of the electrolyte and the electrode is exposed, thus obtaining MoS 2 -PPy//PVA-PMA-SA-TA//MoS 2 -PPy integrated supercapacitor.
Step three: preparation of PPy// PVA-PMA-SA-TA// PPy integrated supercapacitor
(1) Pyrrole Py is added into sulfuric acid solution with the mol/L of 0.5, the mol ratio of Py to sulfuric acid is 1:1.25, and ultrasonic dissolution is used for 30 minutes;
(2) Cutting self-healing PVA-PMA-SA-TA hydrogel into a hydrogel with 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 sulfuric acid solution with the concentration of 0.5mol/L, wherein the molar ratio of the ammonium persulfate to the pyrrole is 1:1, the molar ratio of the ammonium persulfate to the sulfuric acid is 1:1.25, and dissolving for 30 minutes by using ultrasonic;
(4) Taking out the hydrogel in the step III (2), putting the hydrogel into the solution in the step III (3) for polymerization reaction, and placing the solution in an environment of 0-4 ℃.
(5) After 4 hours of in-situ polymerization reaction, the electrode PPy fully grows on the electrolyte, deionized water and ethanol are used for cleaning surface impurities after the electrolyte is taken out, and after the electrolyte is dried, the peripheral edges are cut off, and interface layering of the electrolyte and the electrode is exposed, so that the PPy// PVA-PMA-SA-TA// PPy integrated supercapacitor can be obtained.
The method for preparing the all-solid asymmetric supercapacitor comprises the following steps:
MoS is carried out 2 -PPy//PVA-PMA-SA-TA//MoS 2 The PPy supercapacitor was cut along the electrolyte to give two symmetrical and only one side polymerized MoS as shown in figure 1 2 PVA-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 two symmetrical hydrogels to make hydrogel surfaceAttaching together, standing for 1-3 hours, and obtaining the electrolyte PVA-PMA-SA-TA and the anode MoS through the self-healing property of the PVA-PMA-SA-TA hydrogel 2 PPy, the cathode is 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 illustrates an assembly process of an integrated asymmetric supercapacitor.
Detailed Description
For a better understanding of the present invention, reference will now be made to the following description of the invention taken in conjunction with the accompanying drawings and specific examples
As shown in fig. 1, the assembly process of the integrated asymmetric supercapacitor includes two steps, in which MoS 2 The PPy electrode 1 and the PVA-PMA-SA-TA electrolyte 2 form MoS 2 -PPy//PVA-PMA-SA-TA//MoS 2 The PPy super capacitor, the PPy electrode 3 and the PVA-PMA-SA-TA electrolyte 2 form the PPy// PVA-PMA-SA-TA// PPy super capacitor. Cutting two super capacitors along electrolyte to obtain two symmetrical PVA-PMA-SA-TA hydrogels with PPy polymerized on one side and two symmetrical PVA-PMA-SA-TA hydrogels with MoS polymerized on one side 2 Taking out two symmetrical hydrogel halves of PVA-PMA-SA-TA hydrogel of PPy, adhering the hydrogel surfaces together, standing for 1-3 hr to obtain PVA-PMA-SA-TA as electrolyte and MoS as anode 2 PPy, the cathode is an asymmetric supercapacitor of PPy.
The first embodiment is as follows:
1g of polyvinyl alcohol PVA was dissolved in 10mL of deionized water, and after stirring at 95℃for 2 hours, the solution was clear and transparent. 0.15g of sodium alginate SA and 1.5g of methacrylic acid MA were dissolved in the PVA solution and stirred for 3 hours. Slowly adding 1.5g 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 the reaction, naturally cooling, and freeze-drying by a freeze dryer. The freeze-dried gel was immersed in 5wt.% tannic acid for 24 hours at room temperature. Thus obtaining PVA-PMA-SA-TA hydrogel.
Will be 0.16g MoS 2 And 0.275mL of pyrrole Py was added to 10mL of 0.5mol/L sulfuric acid solution and dissolved using ultrasound for 30 minutes. PVA-PMA-SA-TA hydrogel is cut into cubes with length, width and height of 2cm, 2cm and 0.5cm, and the cubes are put into the obtained solution and kept stand for 20 minutes. 0.912g of ammonium persulfate was dissolved in 10mL of a 0.5mol/L sulfuric acid solution, and dissolved using ultrasound for 30 minutes. 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 for polymerization reaction, and placing the solution in an environment of 0 ℃. After 4 hours of in-situ polymerization, electrode MoS 2 PPy grows on the electrolyte fully, the electrolyte is taken out, deionized water and ethanol are used for cleaning surface impurities, and after drying, the peripheral edge is cut off, the interface layering of the electrolyte and the electrode is exposed, thus obtaining MoS 2 -PPy//PVA-PMA-SA-TA//MoS 2 -PPy integrated supercapacitor.
0.275mL of pyrrole Py was added to 10mL of 0.5mol/L sulfuric acid solution and dissolved using ultrasound for 30 minutes. PVA-PMA-SA-TA hydrogel was cut into cubes with a length, width and height of 2cm, 2cm and 0.5cm, and the cubes were put into the obtained 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 using ultrasound for 30 minutes. 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 for polymerization reaction, and placing the solution in an environment of 0 ℃. After 4 hours of in-situ polymerization reaction, the electrode PPy fully grows on the electrolyte, deionized water and ethanol are used for cleaning surface impurities after the electrolyte is taken out, and after the electrolyte is dried, the peripheral edges are cut off, and interface layering of the electrolyte and the electrode is exposed, so that the PPy// PVA-PMA-SA-TA// PPy integrated supercapacitor can be obtained.
MoS is carried out 2 -PPy//PVA-PMA-SA-TA//MoS 2 The PPy supercapacitor was cut along the electrolyte to give two symmetrical and only one side polymerized MoS as shown in figure 1 2 PVA-PMA-SA-TA hydrogel of PPy.
The PPy// PVA-PMA-SA-TA// PPy super capacitor is cut along the electrolyte,two symmetrical PVA-PMA-SA-TA hydrogels with PPy polymerized on only one side were obtained as shown in FIG. 1. Taking out two symmetrical hydrogels, adhering the hydrogel surfaces together, standing for 1 hr to obtain PVA-PMA-SA-TA with electrolyte PVA-PMA-SA-TA and anode MoS with self-healing property 2 PPy, the cathode is an asymmetric supercapacitor of PPy.
The second embodiment is as follows:
1g of polyvinyl alcohol PVA was dissolved in 10mL of deionized water, and after stirring at 95℃for 2 hours, the solution was clear and transparent. 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 the reaction, naturally cooling, and freeze-drying by a freeze dryer. The freeze-dried gel was immersed in 10wt.% tannic acid for 36 hours at room temperature. Thus obtaining PVA-PMA-SA-TA hydrogel.
Will be 0.32g MoS 2 And 0.275mL of pyrrole Py was added to 10mL of 0.5mol/L sulfuric acid solution and dissolved using ultrasound for 30 minutes. PVA-PMA-SA-TA hydrogel is cut into cubes with length, width and height of 6cm, 6cm and 0.5cm, and the cubes are put into the obtained solution and kept stand for 20 minutes. 0.912g of ammonium persulfate was dissolved in 10mL of a 0.5mol/L sulfuric acid solution, and dissolved using ultrasound for 30 minutes. 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 for polymerization reaction, and placing the solution in an environment of 2 ℃. After 4 hours of in-situ polymerization, electrode MoS 2 PPy grows on the electrolyte fully, the electrolyte is taken out, deionized water and ethanol are used for cleaning surface impurities, and after drying, the peripheral edge is cut off, the interface layering of the electrolyte and the electrode is exposed, thus obtaining MoS 2 -PPy//PVA-PMA-SA-TA//MoS 2 -PPy integrated supercapacitor.
0.275mL of pyrrole Py was added to 10mL of 0.5mol/L sulfuric acid solution and dissolved using ultrasound for 30 minutes. PVA-PMA-SA-TA hydrogel was cut into cubes of 6cm long, 6cm wide and 0.5cm high, and placed in the resulting solution for 20 minutes. 0.912g of ammonium persulfate was dissolved in 10mL of a 0.5mol/L sulfuric acid solution, and dissolved using ultrasound for 30 minutes. 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 for polymerization reaction, and placing the solution in an environment of 2 ℃. After 4 hours of in-situ polymerization reaction, the electrode PPy fully grows on the electrolyte, deionized water and ethanol are used for cleaning surface impurities after the electrolyte is taken out, and after the electrolyte is dried, the peripheral edges are cut off, and interface layering of the electrolyte and the electrode is exposed, so that the PPy// PVA-PMA-SA-TA// PPy integrated supercapacitor can be obtained.
MoS is carried out 2 -PPy//PVA-PMA-SA-TA//MoS 2 The PPy supercapacitor was cut along the electrolyte to give two symmetrical and only one side polymerized MoS as shown in figure 1 2 PVA-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 two symmetrical hydrogels, adhering the hydrogel surfaces together, standing for 2 hr to obtain PVA-PMA-SA-TA with electrolyte PVA-PMA-SA-TA and anode MoS with self-healing property 2 PPy, the cathode is an asymmetric supercapacitor of PPy.
And a third specific embodiment:
1g of polyvinyl alcohol PVA was dissolved in 10mL of deionized water, and after stirring at 95℃for 2 hours, the solution was clear and transparent. 0.25g of sodium alginate SA and 2.5g of methacrylic acid MA were dissolved in the PVA solution and stirred for 3 hours. Slowly adding 2.5g 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 the reaction, naturally cooling, and freeze-drying by a freeze dryer. The freeze-dried gel was immersed in 15wt.% tannic acid for 48 hours at room temperature. Thus obtaining PVA-PMA-SA-TA hydrogel.
Will be 0.64g MoS 2 And 0.275mL of pyrrole Py was added to 10mL of 0.5mol/L sulfuric acid solution and dissolved using ultrasound for 30 minutes. Cutting PVA-PMA-SA-TA hydrogel into a piece with length, width and height of 10cm and 10cm,A0.5 cm 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 using ultrasound for 30 minutes. 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 for polymerization reaction, and placing the solution in an environment of 4 ℃. After 4 hours of in-situ polymerization, electrode MoS 2 PPy grows on the electrolyte fully, the electrolyte is taken out, deionized water and ethanol are used for cleaning surface impurities, and after drying, the peripheral edge is cut off, the interface layering of the electrolyte and the electrode is exposed, thus obtaining MoS 2 -PPy//PVA-PMA-SA-TA//MoS 2 -PPy integrated supercapacitor.
0.275mL of pyrrole Py was added to 10mL of 0.5mol/L sulfuric acid solution and dissolved using ultrasound for 30 minutes. PVA-PMA-SA-TA hydrogel was cut into cubes of 10cm length, 10cm width and 0.5cm height, and 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 using ultrasound for 30 minutes. 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 for polymerization reaction, and placing the solution in an environment of 4 ℃. After 4 hours of in-situ polymerization reaction, the electrode PPy fully grows on the electrolyte, deionized water and ethanol are used for cleaning surface impurities after the electrolyte is taken out, and after the electrolyte is dried, the peripheral edges are cut off, and interface layering of the electrolyte and the electrode is exposed, so that the PPy// PVA-PMA-SA-TA// PPy integrated supercapacitor can be obtained.
MoS is carried out 2 -PPy//PVA-PMA-SA-TA//MoS 2 The PPy supercapacitor was cut along the electrolyte to give two symmetrical and only one side polymerized MoS as shown in figure 1 2 PVA-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 two symmetrical hydrogels, adhering the hydrogel surfaces together, standing for 3 hr to obtain PVA-PMA-SA-TA with electrolyte PVA-PMA-SA-TA and anode MoS with self-healing property 2 -PPy, cathode isAn asymmetric supercapacitor of PPy.
Claims (3)
1. The method for assembling the self-healing gel-based asymmetric supercapacitor is characterized by comprising the following steps of: the method comprises the following steps:
step one: preparation of self-healing PVA-PMA-SA-TA hydrogel electrolyte;
(1) Dissolving polyvinyl alcohol PVA into deionized water, stirring for 2 hours at 95 ℃, and clarifying and transparentizing the 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, a step of;
(3) Adding sodium persulfate APS into the solution prepared in the step (2), wherein the mass ratio of the APS to the MA is 1:1, and reacting the solution at 60 ℃ for 2 hours to polymerize methacrylic acid MA into polymethyl methacrylate PMA; taking out after the reaction, naturally cooling, and freeze-drying by a freeze dryer;
(4) Soaking the gel after freeze drying in 5-15wt.% tannic acid for 24-48 hours at room temperature to obtain PVA-PMA-SA-TA hydrogel;
step two: moS (MoS) 2 -PPy//PVA-PMA-SA-TA//MoS 2 -preparation of a PPy integrated symmetric supercapacitor;
step three: preparation of PPy// PVA-PMA-SA-TA// PPy integrated supercapacitor
Step four: moS is carried out 2 -PPy//PVA-PMA-SA-TA//MoS 2 The PPy supercapacitor is cut along the electrolyte to obtain two symmetrical and only one side is polymerized with MoS 2 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 two symmetrical hydrogels, adhering the hydrogel surfaces together, standing for 1-3 hr, and obtaining electrolysis by self-healing property of PVA-PMA-SA-TA hydrogelThe mass is PVA-PMA-SA-TA, and the anode is MoS 2 PPy, the cathode is an asymmetric supercapacitor of PPy.
2. The method for assembling a self-healing gel-based asymmetric supercapacitor according to claim 1, wherein:
the MoS 2 -PPy//PVA-PMA-SA-TA//MoS 2 -preparation of a PPy integrated symmetric supercapacitor; the method specifically comprises the following steps:
(1) Molybdenum disulfide MoS 2 Adding the powder and pyrrole Py into 0.5mol/L sulfuric acid solution, moS 2 And Py is 1 (1-4), the mole ratio of Py to sulfuric acid is 1:1.25, and ultrasonic dissolution is used for 30 minutes;
(2) Cutting self-healing PVA-PMA-SA-TA hydrogel into a hydrogel with 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 sulfuric acid solution with the concentration of 0.5mol/L, wherein the molar ratio of the ammonium persulfate to the pyrrole is 1:1, the molar ratio of the ammonium persulfate to the sulfuric acid is 1:1.25, and dissolving for 30 minutes by using ultrasonic;
(4) Taking out the hydrogel in the second step (2), putting the hydrogel into the solution in the second step (3) for polymerization reaction, and placing the solution in an environment of 0-4 ℃;
(5) After 4 hours of in-situ polymerization, electrode MoS 2 PPy grows on the electrolyte fully, the electrolyte is taken out, deionized water and ethanol are used for cleaning surface impurities, and after drying, the peripheral edge is cut off, the interface layering of the electrolyte and the electrode is exposed, thus obtaining MoS 2 -PPy//PVA-PMA-SA-TA//MoS 2 -PPy integrated supercapacitor.
3. The method for assembling a self-healing gel-based asymmetric supercapacitor according to claim 1, wherein: the preparation method of the PPy// PVA-PMA-SA-TA// PPy integrated supercapacitor specifically comprises the following steps:
(1) Pyrrole Py is added into sulfuric acid solution with the mol/L of 0.5, the mol ratio of Py to sulfuric acid is 1:1.25, and ultrasonic dissolution is used for 30 minutes;
(2) Cutting self-healing PVA-PMA-SA-TA hydrogel into a hydrogel with 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 sulfuric acid solution with the concentration of 0.5mol/L, wherein the molar ratio of the ammonium persulfate to the pyrrole is 1:1, the molar ratio of the ammonium persulfate to the 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 of 0-4 ℃;
(5) After 4 hours of in-situ polymerization reaction, the electrode PPy fully grows on the electrolyte, deionized water and ethanol are used for cleaning surface impurities after the electrolyte is taken out, and after the electrolyte is dried, the peripheral edges are cut off, and interface layering of the electrolyte and the electrode is exposed, so that the PPy// PVA-PMA-SA-TA// PPy integrated supercapacitor can be obtained.
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| WO2019221490A1 (en) * | 2018-05-15 | 2019-11-21 | 주식회사 엘지화학 | Microcapsules, separator comprising same and electrochemical device comprising same |
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| CN109755043A (en) * | 2019-03-15 | 2019-05-14 | 武汉工程大学 | Self-healing integration gel state supercapacitor and preparation method thereof |
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