CN110265232B - Self-healing hydrogel electrolyte film and preparation method and application thereof - Google Patents
Self-healing hydrogel electrolyte film and preparation method and application thereof Download PDFInfo
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- 239000000017 hydrogel Substances 0.000 title claims abstract description 85
- 239000003792 electrolyte Substances 0.000 title claims abstract description 65
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- 239000000178 monomer Substances 0.000 claims abstract description 21
- 239000012528 membrane Substances 0.000 claims abstract description 15
- BCAIDFOKQCVACE-UHFFFAOYSA-N 3-[dimethyl-[2-(2-methylprop-2-enoyloxy)ethyl]azaniumyl]propane-1-sulfonate Chemical compound CC(=C)C(=O)OCC[N+](C)(C)CCCS([O-])(=O)=O BCAIDFOKQCVACE-UHFFFAOYSA-N 0.000 claims abstract description 11
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims abstract description 11
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 38
- 239000007864 aqueous solution Substances 0.000 claims description 33
- 239000010408 film Substances 0.000 claims description 25
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 19
- 239000000243 solution Substances 0.000 claims description 18
- 229920000642 polymer Polymers 0.000 claims description 10
- 239000003999 initiator Substances 0.000 claims description 9
- 230000008961 swelling Effects 0.000 claims description 9
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 6
- 239000002253 acid Substances 0.000 claims description 6
- 239000003513 alkali Substances 0.000 claims description 6
- 230000002209 hydrophobic effect Effects 0.000 claims description 6
- 238000006116 polymerization reaction Methods 0.000 claims description 6
- 239000012266 salt solution Substances 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 4
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 claims description 4
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 4
- 239000011521 glass Substances 0.000 claims description 4
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 claims description 4
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 claims description 4
- 239000010409 thin film Substances 0.000 claims description 4
- 230000002378 acidificating effect Effects 0.000 claims description 3
- 150000003839 salts Chemical class 0.000 claims description 3
- 229920000144 PEDOT:PSS Polymers 0.000 claims description 2
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 2
- INHCSSUBVCNVSK-UHFFFAOYSA-L lithium sulfate Inorganic materials [Li+].[Li+].[O-]S([O-])(=O)=O INHCSSUBVCNVSK-UHFFFAOYSA-L 0.000 claims description 2
- 239000001103 potassium chloride Substances 0.000 claims description 2
- 235000011164 potassium chloride Nutrition 0.000 claims description 2
- OTYBMLCTZGSZBG-UHFFFAOYSA-L potassium sulfate Chemical compound [K+].[K+].[O-]S([O-])(=O)=O OTYBMLCTZGSZBG-UHFFFAOYSA-L 0.000 claims description 2
- 229910052939 potassium sulfate Inorganic materials 0.000 claims description 2
- 235000011151 potassium sulphates Nutrition 0.000 claims description 2
- 239000011780 sodium chloride Substances 0.000 claims description 2
- 229910052938 sodium sulfate Inorganic materials 0.000 claims description 2
- 235000011152 sodium sulphate Nutrition 0.000 claims description 2
- RBTVSNLYYIMMKS-UHFFFAOYSA-N tert-butyl 3-aminoazetidine-1-carboxylate;hydrochloride Chemical compound Cl.CC(C)(C)OC(=O)N1CC(N)C1 RBTVSNLYYIMMKS-UHFFFAOYSA-N 0.000 claims description 2
- 239000002001 electrolyte material Substances 0.000 claims 1
- 239000000203 mixture Substances 0.000 claims 1
- 150000003384 small molecules Chemical class 0.000 claims 1
- 239000003990 capacitor Substances 0.000 abstract description 10
- 238000004146 energy storage Methods 0.000 abstract description 6
- 238000000034 method Methods 0.000 abstract description 4
- 238000002791 soaking Methods 0.000 description 9
- 238000003756 stirring Methods 0.000 description 7
- 238000007599 discharging Methods 0.000 description 6
- 229920001609 Poly(3,4-ethylenedioxythiophene) Polymers 0.000 description 5
- 238000004132 cross linking Methods 0.000 description 5
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 239000011259 mixed solution Substances 0.000 description 4
- 230000004913 activation Effects 0.000 description 3
- 230000000379 polymerizing effect Effects 0.000 description 3
- 239000004372 Polyvinyl alcohol Substances 0.000 description 2
- 229910001870 ammonium persulfate Inorganic materials 0.000 description 2
- 238000005452 bending Methods 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 229920000867 polyelectrolyte Polymers 0.000 description 2
- 229920002451 polyvinyl alcohol Polymers 0.000 description 2
- 235000019422 polyvinyl alcohol Nutrition 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- 238000000137 annealing Methods 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000010382 chemical cross-linking Methods 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 229920006273 intrinsic self-healing polymer Polymers 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000021715 photosynthesis, light harvesting Effects 0.000 description 1
- -1 polytetrafluoroethylene Polymers 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 238000010526 radical polymerization reaction Methods 0.000 description 1
- 230000008439 repair process Effects 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 230000000638 stimulation Effects 0.000 description 1
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- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/02—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques
- C08J3/03—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques in aqueous media
- C08J3/075—Macromolecular gels
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- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
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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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- C08J2333/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers
- C08J2333/04—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers esters
- C08J2333/14—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers esters of esters containing halogen, nitrogen, sulfur, or oxygen atoms in addition to the carboxy oxygen
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- C08K3/00—Use of inorganic substances as compounding ingredients
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Abstract
The invention relates to a self-healing hydrogel electrolyte film and a preparation method and application thereof. The electrolyte film is prepared by copolymerizing [2- (methacryloyloxy) ethyl ] dimethyl- (3-sulfopropyl) ammonium hydroxide and methacrylic acid monomers. The hydrogel electrolyte membrane of the present invention not only has very high tensile strength, but also exhibits excellent repeatable self-healing properties, as compared to the prior art. The hydrogel film is used as an electrolyte, and a pre-stretching method is used for constructing a corrugated electrode on the surface of the hydrogel electrolyte film; the flexible super capacitor prepared by the method has good stretchability (1000%) and self-healing performance, and the healed super capacitor has the energy storage performance consistent with that of the original device. The high-tensile self-healing super capacitor disclosed by the invention is simpler in structure and preparation process, and has a wide application prospect in the field of flexible stretchable electronic devices.
Description
Technical Field
The invention belongs to the technical field of photoelectric materials, and particularly relates to a self-healing hydrogel electrolyte film, and a preparation method and application thereof.
Background
In recent years, flexible wearable electronic devices such as electronic skins, smart fabrics, implantable medical devices, and the like have received much attention, and thus the demand for wearable flexible energy storage devices has increased. Wearable flexible energy storage devices require that the related devices have excellent flexibility and stable electrochemical performance under deformation conditions. The super capacitor is used as one of the energy storage devices, has higher energy density and power density, and has excellent cycle stability and rapid charge and discharge performance, so that the flexible super capacitor device has wide application prospect in the fields of portable electronic products and flexible wearable electronic devices. However, as an important component in flexible supercapacitors, the preparation of flexible, stretchable, self-healing hydrogel electrolytes still faces significant challenges. The hydrogel electrolyte commonly used by the flexible supercapacitor at present mainly takes polyvinyl alcohol as a base material, and has the advantages of good water solubility and wider pH application range. However, the hydrogel electrolytes based on polyvinyl alcohols have not high mechanical properties, neither intrinsic self-healing properties nor high tensile properties.
At present, for a hydrogel electrolyte, a self-healing function is realized mainly by introducing dynamic non-covalent bonds, and the dynamic non-covalent bonds commonly used as cross-linking points include hydrogen bonds, coordination bonds and the like, but the self-healing performance of the hydrogel electrolyte obtained by adopting the dynamic non-covalent bonds as a cross-linking mode is poor, and the cycle times of fracture/repair are small. Compared with a covalent crosslinking mode, the dynamic non-covalent bond is easy to be damaged as a main energy dissipation point under a stretching condition due to lower energy, and cannot meet the requirement of large deformation of related devices. Therefore, research on hydrogel electrolytes having high strength and self-healing properties is particularly important.
Disclosure of Invention
The technical problem is as follows: aiming at the defects of the prior art, the invention provides a self-healing hydrogel electrolyte film and a preparation method and application thereof.
The technical scheme is as follows: in order to solve the problems, the invention adopts the following technical scheme:
the invention provides a self-healing hydrogel electrolyte, which is a physically crosslinked hydrogel and contains a polymer chain segment formed by micromolecule polymerization and an electrolyte aqueous solution; wherein the polymer chain segments are connected with each other through hydrophobic association to form a three-dimensional network structure, and an electrolyte aqueous solution is filled in gaps of the three-dimensional network structure; the polymer chain segment is obtained by copolymerizing two monomer molecules of [2- (methacryloyloxy) ethyl ] dimethyl- (3-sulfopropyl) ammonium hydroxide and methacrylic acid; the electrolyte aqueous solution is acidic, alkaline or salt electrolyte aqueous solution.
In the self-healing hydrogel electrolyte, polymer chain segments obtained by copolymerizing two monomer molecules of [2- (methacryloyloxy) ethyl ] dimethyl- (3-sulfopropyl) ammonium hydroxide and methacrylic acid do not contain chemical crosslinking, and the self-healing hydrogel electrolyte needs to be soaked in the electrolyte aqueous solution for a certain time after polymerization is completed. The soaking step introduces electrolyte on one hand, and introduces electrostatic shielding to enable hydrophobic parts in polymer chain segments to form cross-linking points due to hydrophobic association so as to endow hydrogel with better mechanical property and self-healing property on the other hand.
The invention also provides a preparation method of the self-healing hydrogel electrolyte film, which is characterized by comprising the following steps:
(1) dispersing two polymerizable monomers of [2- (methacryloyloxy) ethyl ] dimethyl- (3-sulfopropyl) ammonium hydroxide and methacrylic acid in water to obtain a monomer aqueous solution;
(2) adding an initiator into the monomer aqueous solution for polymerization reaction to obtain hydrogel C;
(3) and swelling the hydrogel C in acid liquor, alkali liquor or salt solution until the hydrogel C is balanced to obtain the self-healing hydrogel electrolyte film. Preferably, the total mass concentration of the two polymerizable monomers in the step (1) is 25 to 50 percent.
Preferably, the mass ratio of the two polymerizable monomers of [2- (methacryloyloxy) ethyl ] dimethyl- (3-sulfopropyl) ammonium hydroxide and methacrylic acid in the step (1) is 0.2-1.
Preferably, the initiator in the step (2) is a thermal initiator or a photoinitiator, and the mass concentration is 0.05-0.5%.
Preferably, the acidic electrolyte aqueous solution in step (3) is one or more of sulfuric acid, phosphoric acid, hydrochloric acid, perchloric acid aqueous solution; the alkaline electrolyte is one or two of sodium hydroxide and potassium hydroxide aqueous solutions, and the salt electrolyte aqueous solution is one of potassium chloride, lithium chloride, sodium chloride, potassium sulfate, lithium sulfate and sodium sulfate aqueous solutions; the molar concentration of the acid liquor, the alkali liquor or the salt solution is 0.1-12M.
Preferably, the swelling time in the step (3) is 12-48 hours until the swelling is balanced.
Use of a self-healing hydrogel electrolyte membrane as described above for the electrolyte of a flexible stretchable supercapacitor consisting of a hydrogel electrolyte membrane and a thin film electrode covering both sides of the membrane,
preferably, the material of the thin film electrode is PEDOT: PSS film.
Compared with the prior art, the beneficial effects of the invention are embodied in the following aspects:
(1) the hydrogel polyelectrolyte film has high tensile property and excellent repeatable self-healing performance;
(2) the super capacitor has good flexibility and repeatable bending property;
(3) the super capacitor of the invention shows ultra-high (1000%) tensile property and self-healing property.
Drawings
FIG. 1 is a stress-strain curve of hydrogel after soaking in phosphoric acid solutions of different molarity in example 2 of the present invention;
FIG. 2 is a graph showing the change in activation energy of hydrogels obtained in example 2 of the present invention after soaking in phosphoric acid solutions of different molarity;
FIG. 3 shows capacitance values of the supercapacitor prepared in example 3 of the present invention under different charging and discharging conditions;
FIG. 4 shows the capacitance values of the supercapacitor prepared in example 3 of the present invention under different tensile conditions;
FIG. 5 shows the capacitance values of the supercapacitor prepared in example 4 of the present invention after soaking in phosphoric acid solutions of different molarity.
Detailed Description
In order to make the description of the object, technical solution and product advantages of the present invention more clear, the present invention is further described in detail below with reference to the embodiments and the related drawings. It should be understood that the following specific examples are illustrative only and are not intended to limit the invention.
In order to achieve the purpose, the invention provides a self-healing hydrogel electrolyte film and a preparation method thereof. The self-healing hydrogel electrolyte film has wide application prospect in flexible electronic devices such as flexible stretchable supercapacitors and the like.
The preparation method of the self-healing hydrogel electrolyte film comprises the following steps:
(1) dispersing [2- (methacryloyloxy) ethyl ] dimethyl- (3-sulfopropyl) ammonium hydroxide and methacrylic acid in deionized water, and stirring at the rotating speed of 200-500 rpm/min at the temperature of 22-26 ℃ until a uniform and transparent solution A is obtained;
(2) adding a thermal initiator into the solution A in the step (1), and stirring at the rotating speed of 200-500 rpm/min at the temperature of 22-26 ℃ until a uniform and transparent solution B is obtained;
(3) injecting the solution B in the step (2) into a glass mold with the interval of 500-1500 mu m, and polymerizing for 5-8 hours at the temperature of 55-65 ℃ to obtain hydrogel C;
(4) and swelling the hydrogel C in acid liquor, alkali liquor or salt solution for 12-48 hours until the hydrogel C is balanced to obtain the self-healing hydrogel electrolyte film.
Example 1
Preparation of self-healing hydrogel electrolyte film
Step (1): 0.5g of [2- (methacryloyloxy) ethyl ] dimethyl- (3-sulfopropyl) ammonium hydroxide (DMAPS) monomer was added to 3ml of water;
step (2): adding 2g of methacrylic acid (AAc) into the solution obtained in the step 1, and stirring at the rotating speed of 200-500 rpm/min for more than 10min to obtain a uniform and transparent monomer aqueous solution.
And (3): and (3) adding 0.0126g of ammonium persulfate as an initiator into the mixed solution in the step (2), and stirring for 10 minutes.
And (4): and (4) injecting the mixed solution obtained in the step (3) into a glass mold with the interval of 1000 mu m by using a liquid transfer gun, and polymerizing for 6 hours at the temperature of 60 ℃ to obtain the hydrogel.
And (5): and (4) swelling the hydrogel obtained in the step (4) in 1M phosphoric acid aqueous solution for 24 hours until the hydrogel is balanced to obtain the self-healing hydrogel electrolyte.
Through the steps, the self-healing polyelectrolyte hydrogel obtained through free radical polymerization has excellent stretchability (5000%), and also shows good self-healing performance, and the hydrogel can recover to a certain strength before fracture at room temperature after being mutually contacted after being cut off, without any external stimulation. The self-healing properties of hydrogels can be attributed to the presence of a large number of hydrogen bonds and ionic associations on the polymer chains. The hydrogel can be used as an electrolyte after being soaked in a phosphoric acid solution, compared with the common H3PO4PVA has excellent energy storage effect.
Example 2
Preparation of self-healing hydrogel electrolyte film
Example 1 was repeated with the same procedure except that the soaking was performed by changing the phosphoric acid aqueous solution of different concentrations in said step (5) to obtain hydrogels soaked in different concentrations.
Through the steps, after the hydrogel is soaked in phosphoric acid aqueous solutions with different concentrations, the modulus and the volume of the hydrogel are changed, the modulus of the hydrogel is larger and larger along with the increase of the concentration of phosphoric acid, and the stretchability is poorer and poorer, as shown in fig. 1, the stress-strain curve of the hydrogel after being soaked in the phosphoric acid solutions with different molar concentrations can be stretched to 50 times of the original stress-strain curve at 1M, and the tensile modulus is 0.01 MPa; when the concentration reaches 4M, the hydrogel can be stretched to 25 times of the original one, and the tensile modulus is 0.2 MPa; when soaked in a low concentration phosphoric acid aqueous solution, the volume swells, almost in a fluid state. FIG. 2 is a graph showing the change of activation energy of a hydrogel after soaking in phosphoric acid solutions with different molar concentrations, and the apparent activation energy of the hydrogel increases with the increase of the concentration of the soaked phosphoric acid, which is mainly because the hydrogel is physically crosslinked, and the lack of a crosslinking agent among polymer chains leads hydrophobic parts in the polymer chain segments to form crosslinking points due to hydrophobic association by introducing an electrostatic shield so as to endow the hydrogel with better mechanical properties.
Example 3
Preparation of flexible solid-state supercapacitor
Step (1): 0.25g of [2- (methacryloyloxy) ethyl ] dimethyl- (3-sulfopropyl) ammonium hydroxide (DMAPS) monomer was added to 1.5ml of water;
step (2): adding 1g of methacrylic acid (AAc) into the solution obtained in the step 1, stirring at the rotating speed of 200-500 rpm/min for more than 10min to obtain a uniform and transparent monomer aqueous solution.
And (3): and (3) adding 0.0063g of ammonium persulfate into the mixed solution in the step (2), and stirring for 10 minutes.
And (4): and (4) injecting the mixed solution obtained in the step (3) into a glass mold with the interval of 1000 mu m by using a liquid transfer gun, and polymerizing for 6 hours at the temperature of 60 ℃ to obtain the hydrogel.
And (5): and (4) swelling the hydrogel in the 1M phosphoric acid aqueous solution for 24 hours until the hydrogel is balanced to obtain the self-healing hydrogel electrolyte film.
And (6): and mixing the PEDOT, namely PSS aqueous solution and a certain amount of PEO solution, uniformly stirring, dripping into a polytetrafluoroethylene mold to form a film, annealing and drying to obtain the PEDOT flexible electrode film.
And (7): and (3) cutting the PEDOT film obtained in the step (6) into a strip shape with the size of 20mm multiplied by 10mm, connecting copper wires at the tail ends by silver colloid, covering a PEDOT electrode respectively, and obtaining the supercapacitor by covering two sides of the hydrogel electrolyte film obtained in the step (5).
Through the steps, the pseudocapacitance material PEDOT is introduced to prepare the super capacitor with the performance of 9.7mF/cm2. FIG. 3 shows the capacitance values of the prepared super capacitor measured under different charging and discharging conditions, and FIG. 4 shows the capacitance values of the prepared super capacitor measured under different charging and discharging conditionsCapacitance values under different tensile conditions.
Example 4
Preparation of flexible solid-state supercapacitor
Example 3 was repeated with the same procedure except that the soaking was performed by changing the phosphoric acid aqueous solution of different concentrations in said step (5) to obtain hydrogels soaked in different concentrations.
Through the steps, the optimal performance of the prepared flexible supercapacitor is determined to be the soaking of 0.5M phosphoric acid solution, as shown in FIG. 5, and the charging and discharging time is 47 s; when the phosphoric acid with the concentration of 0.1M is soaked, the charging and discharging time is reduced to 40 s; when the concentration of the soaked phosphoric acid is increased to be 1M, 2M and 4M, the charging and discharging time is 44s, 43s and 40s respectively; the hydrogel without soaking has almost no energy storage property and is not suitable as an electrolyte.
In general, the self-healing hydrogel electrolyte film prepared by the invention has excellent mechanical properties, and the flexible supercapacitor prepared by using the self-healing hydrogel electrolyte film as an electrolyte has high stretching and bending capabilities, also has self-healing performance and has wide application prospects in flexible electronic devices.
It will be understood by those skilled in the art that the foregoing is only a preferred embodiment of the present invention, and is not intended to limit the invention, and that any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the scope of the present invention.
Claims (9)
1. A self-healing hydrogel electrolyte film is characterized in that the hydrogel electrolyte film is a physically cross-linked hydrogel which comprises a polymer chain segment formed by polymerization of small molecules and an electrolyte aqueous solution; wherein, the polymer chain segments are connected with each other through hydrophobic association to form a three-dimensional network structure, and the electrolyte aqueous solution is filled in the gaps of the three-dimensional network structure; the macromolecular chain segment is obtained by copolymerizing two monomer molecules of [2- (methacryloyloxy) ethyl ] dimethyl- (3-sulfopropyl) ammonium hydroxide and methacrylic acid; the electrolyte aqueous solution is acidic or alkaline or salt electrolyte aqueous solution;
the preparation method of the self-healing hydrogel electrolyte film comprises the following steps:
(1) dispersing two polymerizable monomers of [2- (methacryloyloxy) ethyl ] dimethyl- (3-sulfopropyl) ammonium hydroxide and methacrylic acid in water to obtain a monomer aqueous solution A;
(2) adding an initiator into the monomer aqueous solution A to perform polymerization reaction to obtain hydrogel C;
(3) swelling the obtained hydrogel C in acid liquor or alkali liquor or salt solution until the hydrogel C is balanced to obtain the self-healing hydrogel electrolyte film.
2. A self-healing hydrogel electrolyte membrane according to claim 1, wherein the total concentration of the two polymerizable monomers in step (1) is 25-50% by mass.
3. The self-healing hydrogel electrolyte membrane according to claim 1, wherein the mass ratio of the two polymerizable monomers of [2- (methacryloyloxy) ethyl ] dimethyl- (3-sulfopropyl) ammonium hydroxide and methacrylic acid in step (1) is 0.2-1: 1.
4. A self-healing hydrogel electrolyte membrane according to claim 1, wherein the initiator in the step (2) is a thermal initiator or a photoinitiator, and the mass concentration is 0.1% to 0.5%.
5. A self-healing hydrogel electrolyte membrane according to claim 1, wherein the acid solution in step (3) is one or more of sulfuric acid, phosphoric acid, hydrochloric acid, perchloric acid aqueous solution; the alkali liquor is one or two of sodium hydroxide and potassium hydroxide aqueous solutions; the salt solution is one of potassium chloride, lithium chloride, sodium chloride, potassium sulfate, lithium sulfate and sodium sulfate aqueous solution; the molar concentration of the acid liquor, the alkali liquor or the salt solution is 0.1-12M.
6. The self-healing hydrogel electrolyte membrane according to claim 1, wherein in the step (1), the mixture is stirred at a rotation speed of 200rpm/min to 500rpm/min at a temperature of 22 ℃ to 26 ℃ until a uniform and transparent monomer aqueous solution A is obtained.
7. The self-healing hydrogel electrolyte membrane according to claim 1, wherein in the step (2), after the initiator is added to the monomer aqueous solution a, the monomer aqueous solution a is stirred at a rotation speed of 200rpm/min to 500rpm/min at a temperature of 22 to 26 ℃ until a uniform and transparent solution B is obtained, the solution B is injected into a glass mold with an interval of 500 μm to 1500 μm, and the polymerization is carried out at a temperature of 55 ℃ to 65 ℃ for 5 to 8 hours, so as to obtain the hydrogel C.
8. A self-healing hydrogel electrolyte membrane according to claim 1, wherein the swelling time in step (3) is 12-48 hours until swelling equilibrium.
9. The use of the self-healing hydrogel electrolyte membrane according to claim 1, wherein the self-healing hydrogel electrolyte membrane is used as an electrolyte material in a flexible stretchable supercapacitor and the flexible stretchable supercapacitor consists of a hydrogel electrolyte membrane and a thin film electrode covering both sides of the hydrogel electrolyte membrane; the thin film electrode is made of PEDOT: PSS film.
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CN111261425B (en) * | 2020-02-07 | 2022-02-08 | 齐鲁工业大学 | Antifreeze hydrogel solid electrolyte, preparation method and application in supercapacitor |
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CN113571343A (en) * | 2021-06-17 | 2021-10-29 | 南京邮电大学 | Integrated super capacitor and preparation method thereof |
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