CN116217968A - Supermolecular hydrogel electrolyte and preparation method and application thereof - Google Patents
Supermolecular hydrogel electrolyte and preparation method and application thereof Download PDFInfo
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- 239000003792 electrolyte Substances 0.000 title claims abstract description 98
- 238000002360 preparation method Methods 0.000 title claims abstract description 31
- 239000000178 monomer Substances 0.000 claims abstract description 106
- 150000003839 salts Chemical class 0.000 claims abstract description 43
- 239000007864 aqueous solution Substances 0.000 claims abstract description 41
- 238000000034 method Methods 0.000 claims abstract description 17
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 7
- 238000002791 soaking Methods 0.000 claims abstract description 6
- 239000000243 solution Substances 0.000 claims description 50
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical group [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 28
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 26
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 26
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 claims description 26
- 238000003756 stirring Methods 0.000 claims description 26
- -1 3- (methacrylamido) propyl Chemical group 0.000 claims description 25
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 25
- 239000000908 ammonium hydroxide Substances 0.000 claims description 25
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 claims description 25
- 239000011521 glass Substances 0.000 claims description 22
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 13
- 239000003999 initiator Substances 0.000 claims description 9
- 239000012266 salt solution Substances 0.000 claims description 9
- 230000000379 polymerizing effect Effects 0.000 claims description 8
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 5
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 claims description 4
- 239000008151 electrolyte solution Substances 0.000 claims description 4
- 230000008569 process Effects 0.000 claims description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 3
- 229920000144 PEDOT:PSS Polymers 0.000 claims description 3
- 239000002390 adhesive tape Substances 0.000 claims description 3
- 229910052802 copper Inorganic materials 0.000 claims description 3
- 239000010949 copper Substances 0.000 claims description 3
- 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
- 238000004806 packaging method and process Methods 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
- 229920000642 polymer Polymers 0.000 abstract description 10
- 229910052739 hydrogen Inorganic materials 0.000 abstract description 4
- 239000001257 hydrogen Substances 0.000 abstract description 4
- 230000002441 reversible effect Effects 0.000 abstract description 3
- 238000012360 testing method Methods 0.000 description 21
- 239000000463 material Substances 0.000 description 10
- 230000001105 regulatory effect Effects 0.000 description 10
- 230000004044 response Effects 0.000 description 9
- 239000003990 capacitor Substances 0.000 description 8
- 230000002209 hydrophobic effect Effects 0.000 description 8
- 230000003247 decreasing effect Effects 0.000 description 7
- 239000011245 gel electrolyte Substances 0.000 description 7
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- 229910003002 lithium salt Inorganic materials 0.000 description 2
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- 230000004888 barrier function Effects 0.000 description 1
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- 230000008859 change Effects 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 238000002484 cyclic voltammetry Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000002001 electrolyte material Substances 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 229910017053 inorganic salt Inorganic materials 0.000 description 1
- GDOPTJXRTPNYNR-UHFFFAOYSA-N methyl-cyclopentane Natural products CC1CCCC1 GDOPTJXRTPNYNR-UHFFFAOYSA-N 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 230000003938 response to stress Effects 0.000 description 1
- 230000006903 response to temperature Effects 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
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- 238000006467 substitution reaction Methods 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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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—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 a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/04—Acids; Metal salts or ammonium salts thereof
- C08F220/06—Acrylic acid; Methacrylic acid; Metal salts or ammonium salts thereof
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- C08F220/52—Amides or imides
- C08F220/54—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide
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- C08F220/606—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide containing nitrogen in addition to the carbonamido nitrogen and containing other heteroatoms
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Abstract
The invention discloses a supermolecular hydrogel electrolyte, a preparation method and application thereof. The method comprises the steps of mixing monomers PDP and AA in proportion, obtaining supermolecule hydrogel through polymerization reaction, and then soaking in a salt electrolyte aqueous solution to obtain the supermolecule hydrogel electrolyte. The polymer network in the supermolecular hydrogel electrolyte is crosslinked by reversible non-covalent bonds such as hydrogen bonds, so that the supermolecular hydrogel electrolyte has the characteristics of superstretching, self-healing and the like. The invention regulates and controls the mechanical property and the electrochemical property of the hydrogel electrolyte by controlling the mass ratio of the monomer, the concentration of the monomer and the concentration of the aqueous solution of the salt electrolyte, so that the hydrogel electrolyte is suitable for application scenes with different mechanical property and electrochemical property requirements, and has wide application prospect in the field of flexible stretchable electronic devices.
Description
Technical Field
The invention belongs to the technical field of high-molecular photoelectric materials, and relates to a supermolecular hydrogel electrolyte, a preparation method and application thereof.
Background
With the popularization and development of 5G networks and intelligent terminals, wearable electronic equipment with flexible and stretchable characteristics shows great market application prospects. Currently, the application of wearable electronics is embodied in many aspects of human life, such as flexible energy storage devices, wearable physiological detection devices, and the like. Flexible stretchable electronic devices are typically assembled from a flexible electrolyte and flexible electrodes in a "sandwich" configuration. Hydrogel-based electrolyte materials are widely used and studied in the field of flexible solid electrolytes because of their good flexibility and ionic conductivity. Meanwhile, because the hydrogel has good biocompatibility, the hydrogel can coexist with human tissues, thereby exhibiting good wearability.
The traditional hydrogel (DOI: 10.7536/PC 131212) has the problems of single and uneven network structure, lack of energy dissipation mechanism and the like, and has limited mechanical strength, has a large gap from natural tissues, has stretching capability which is only several times that of original length, and has fatigue threshold less than 100J/m 2 . And the polymer network in the polymer is generally crosslinked by covalent bonds, so that the polymer has no self-repairing function and the like, and is easy to permanently destroy to cause the failure of related devices. In addition, most hydrogel electrolytes have poor adhesion (DOI: 10.1021/acsami.7b07639), which is disadvantageous for bonding with electrode materials to form an effective interface to reduce interface resistance, thus exhibiting poor electrochemical performance.
Corresponding technical improvements are made by those skilled in the art to the above problems. For example, chinese patent application CN111952081a discloses a method for preparing an redox gel electrolyte for all solid super capacitors, which uses an amphoteric group-containing monomer [3- (methacrylamido) propyl ] dimethyl (3-thiopropyl) ammonium hydroxide inner salt (PDP) and 2-methyl-2-acrylic acid-2, 6-tetramethyl-4-piperidinyl ester (TEMPO), an initiator and a salt solution to prepare a P (PDP-co-TEMPO) copolymer. The gel electrolyte is subjected to sol-gel conversion at normal temperature, physical gel is formed through dipole-dipole interaction, the gel electrolyte and lithium salt have strong water retention property, the ionic conductivity of the electrolyte is improved through the cooperation of an amphoteric high polymer side chain and the lithium salt, the gel electrolyte has good electrochemical performance, self-discharge performance and cycle performance when being applied to an all-solid-state supercapacitor, and the ion conductivity and the water content of the poly-amphoteric gel electrolyte can be controlled by controlling the amount of inorganic salt lithium chloride. However, the gel electrolyte prepared by the method has the characteristics of low mechanical property, no super-stretching, self-healing and the like because of weak physical bonding effect and weak hydrophobic association effect exerted by the salt solution, and the application in the related fields, particularly the application on flexible electronic products, is obviously limited.
Therefore, it is necessary to further explore and improve the preparation method of the hydrogel electrolyte film so as to comprehensively improve the mechanical properties of the material from multiple angles and meet the use requirements of different application scenes.
Disclosure of Invention
The invention aims to provide a supermolecular hydrogel electrolyte with high mechanical property, and a preparation method and application thereof. The hydrogel electrolyte takes (3- (methacrylamido) propyl) dimethyl (3-thiopropyl) ammonium hydroxide inner salt (PDP) and Acrylic Acid (AA) as monomers, a supermolecule hydrogel is obtained through polymerization reaction, and then the supermolecule hydrogel is soaked in a salt electrolyte aqueous solution, and the mechanical property and the electrochemical property of the hydrogel electrolyte are regulated and controlled in a large range while the electrolyte is introduced. The supermolecular hydrogel electrolyte has good stretchability and self-healing property due to the fact that the internal polymer chains of the supermolecular hydrogel electrolyte are crosslinked in a reversible non-covalent mode; the method has the advantages that the method is used for carrying out soaking treatment in the salt solution, and hydrophobic association can be introduced to further improve the internal network structure of the device, so that the device has high mechanical properties, can meet the use requirements of different scenes, and further expands the working range and application scenes of flexible electronic devices based on hydrogel electrolyte.
The technical scheme for realizing the purpose of the invention is as follows:
the preparation method of the supermolecular hydrogel electrolyte specifically comprises the following steps:
(1) Dissolving (3- (methacrylamido) propyl) dimethyl (3-thiopropyl) ammonium hydroxide inner salt and acrylic acid in water, and uniformly stirring to obtain a monomer aqueous solution;
(2) Adding an initiator into the monomer aqueous solution, and performing polymerization reaction to obtain supermolecule hydrogel;
(3) Soaking the supermolecule hydrogel in the aqueous solution of the salt electrolyte for 24-48 hours to obtain the supermolecule hydrogel electrolyte.
In the step (1), the mechanical property and the electrochemical property of the supermolecule hydrogel electrolyte are regulated and controlled by regulating the total mass concentration of (3- (methacrylamido) propyl) dimethyl (3-thiopropyl) ammonium hydroxide inner salt and acrylic acid in the monomer aqueous solution. As the total mass concentration of (3- (methacrylamido) propyl) dimethyl (3-thiopropyl) ammonium hydroxide inner salt and acrylic acid increases, the fracture strain of the hydrogel increases and then decreases.
In the specific embodiment of the invention, the total mass concentration of the (3- (methacrylamido) propyl) dimethyl (3-thiopropyl) ammonium hydroxide inner salt and the acrylic acid in the monomer aqueous solution is 35-55%. At a total mass concentration of 45%, the breaking strain of the hydrogel was maximum.
In the step (1), the mechanical property and the electrochemical property of the supermolecule hydrogel electrolyte are regulated and controlled by regulating the mass ratio of (3- (methacrylamido) propyl) dimethyl (3-thiopropyl) ammonium hydroxide inner salt and acrylic acid in the monomer aqueous solution. With increasing mass ratio of (3- (methacrylamido) propyl) dimethyl (3-thiopropyl) ammonium hydroxide inner salt to acrylic acid, the fracture strain of the hydrogel increases and then decreases.
In the specific embodiment of the invention, in the aqueous monomer solution, the mass ratio of the (3- (methacrylamido) propyl) dimethyl (3-thiopropyl) ammonium hydroxide inner salt to the acrylic acid is 1:1-1:7. At a mass ratio of 1:5, the breaking strain of the hydrogel was maximum.
In the step (3), the mechanical property and the electrochemical property of the supermolecule hydrogel electrolyte are regulated and controlled by regulating the concentration of the salt electrolyte aqueous solution. With the increase of the concentration of the aqueous solution of the salt electrolyte, the breaking strain of the supermolecular hydrogel electrolyte is firstly increased and then decreased, the elastic modulus is firstly decreased and then increased, and the breaking energy is firstly decreased and then increased.
In a specific embodiment of the present invention, the concentration of the aqueous solution of the salt electrolyte is 0.5M to 6M. The hydrogel fracture strain was maximized at a concentration of 1.5M of the aqueous salt electrolyte solution.
Preferably, in the step (1), the stirring process is as follows: stirring at 22-26 deg.c and 200-500 rpm until homogeneous transparent aqueous monomer solution is obtained.
Preferably, in step (2), the initiator is a thermal initiator or photoinitiator as conventionally used in the art. In a specific embodiment of the present invention, the initiator used is ammonium persulfate. More preferably, the mass concentration of ammonium persulfate is 0.1% to 0.5%.
Preferably, in the step (2), the polymerization reaction is carried out by: after adding an initiator into the monomer aqueous solution, stirring at a rotation speed of 200-500 rpm at 22-26 ℃ until a uniform and transparent solution is obtained, then injecting the solution into a glass mold, and polymerizing at 55-65 ℃ for 5-8 hours to obtain the supermolecule hydrogel.
Preferably, in the step (3), the aqueous salt electrolyte solution is an aqueous salt electrolyte solution commonly used in the art, such as potassium chloride, lithium chloride, sodium chloride, potassium sulfate, lithium sulfate, sodium sulfate aqueous solution, and the like. In a specific embodiment of the present invention, the aqueous solution of a salt electrolyte is an aqueous solution of lithium chloride.
The invention provides the supermolecular hydrogel electrolyte prepared by the preparation method.
The invention also provides an application of the supermolecular hydrogel electrolyte in preparing a flexible stretchable supercapacitor, which comprises the following specific application methods: and (3) attaching PEDOT: PSS electrodes on two sides of the supermolecule hydrogel electrolyte to prepare the flexible stretchable supercapacitor. The conductivity of the flexible stretchable super capacitor prepared by the invention can reach 0.96S/m.
The invention also provides application of the supermolecule hydrogel electrolyte in preparing a flexible resistance sensor, and the specific application method comprises the following steps: copper wires are connected to two sides of the supermolecule hydrogel electrolyte, and VHB adhesive tapes are attached to two sides of the hydrogel electrolyte to complete packaging, so that the flexible resistance sensor is manufactured. The sensor prepared by the invention has sensitive and stable response characteristics under the same stress, different strains and different temperatures.
Compared with the prior art, the invention has the following advantages:
(1) The hydrogel electrolyte prepared by the invention is a physically cross-linked supermolecular hydrogel, which contains a macromolecule chain segment formed by small molecule polymerization and a salt electrolyte aqueous solution, wherein the macromolecule chain segment is obtained by copolymerizing (3- (methacrylamido) propyl) dimethyl (3-thiopropyl) ammonium hydroxide inner salt and acrylic acid two monomer molecules. The mechanical property and the electrochemical property of the electrolyte film material are regulated and controlled by controlling the mass ratio of the monomers, the total concentration of the monomers and the concentration of the salt electrolyte aqueous solution, so that the electrolyte film material is suitable for different application scenes, for example, the elastic modulus of the hydrogel is greatly increased by regulating the mass ratio of the monomers, the total concentration of the monomers and the concentration of the salt electrolyte aqueous solution, and the material can normally work under larger strain and stress conditions;
(2) The polymer network in the supramolecular hydrogel electrolyte prepared by the invention contains zwitterionic polymer chain segments, the polymer chain segments are crosslinked to form a three-dimensional network structure through reversible non-covalent actions such as hydrogen bonds, electrostatic actions, hydrophobic associations and the like, and electrolyte aqueous solution is filled in gaps of the three-dimensional network structure, so that an effective energy dissipation mechanism is provided, and the stretchability of the hydrogel material is improved;
(3) The zwitterionic polymer chain segment in the supramolecular hydrogel electrolyte prepared by the invention contains a large number of charged groups, the charged groups can effectively enhance the interfacial adhesion between the electrode and the gel electrolyte, and the adhesion between the film material and the electrode material is facilitated to form an effective interface to reduce the interfacial impedance, so that the electrochemical performance of the material is remarkably improved;
(4) According to the invention, the supermolecular hydrogel is soaked in a salt solution with a certain concentration, the mechanical property of the hydrogel is further regulated and controlled in a large range through hydrophobic association while the electrolyte is introduced, and the salt solution with a proper concentration is selected to participate in the reaction, so that the conductivity of the supermolecular hydrogel electrolyte can be controlled in a proper range, and the problems of slowing of electron transmission speed and losing of effective adhesion with electrodes caused by too high concentration and enhanced hydrophobic effect are avoided.
Drawings
FIG. 1 is a tensile stress strain diagram of the supramolecular hydrogels prepared in examples 1-6;
FIG. 2 is a graph of tensile stress strain of supramolecular hydrogels prepared in examples 7-10;
FIG. 3 is a graph of tensile stress strain for the supramolecular hydrogel electrolytes prepared in examples 11-16;
FIG. 4 is a graph of the elastic modulus of the supramolecular hydrogel electrolytes prepared in examples 11-16;
FIG. 5 is a graph of the break energy of the supramolecular hydrogel electrolytes prepared in examples 11-16;
FIG. 6 is an ion conductivity graph of the supramolecular hydrogel electrolytes prepared in examples 11-16;
FIG. 7 is a cyclic voltammogram of a flexible supercapacitor made based on the electrolyte prepared in example 13;
FIG. 8 is a constant current charge-discharge plot of a flexible supercapacitor made based on the electrolyte prepared in example 13;
FIG. 9 is an impedance plot of a flexible supercapacitor made based on the electrolyte prepared in example 13;
FIG. 10 is a plot of the repeated response signal of a flexible strain sensor prepared based on the electrolyte prepared in example 13 to the same pressure;
FIG. 11 is a response signal of a flexible strain sensor prepared based on the electrolyte prepared in example 13 to different tensile strain returns;
FIG. 12 is a graph of resistance values of flexible strain sensors prepared based on the electrolyte prepared in example 13 as a function of temperature;
fig. 13 is a graph showing the structural factor GF for a flexible strain sensor prepared on the basis of the electrolyte prepared in example 13 for different strains.
Detailed Description
The following description of the present invention is provided with reference to the accompanying drawings, but is not limited to the following description, and any modifications or equivalent substitutions of the present invention should be included in the scope of the present invention without departing from the spirit and scope of the present invention.
EXAMPLE 1 preparation of supramolecular hydrogel P (AA-co-PDP) (total monomer concentration 45% by mass, monomer mass ratio 1:1)
(1) 1g of (3- (methacrylamido) propyl) dimethyl (3-thiopropyl) ammonium hydroxide inner salt and 1g of acrylic acid are weighed according to the mass ratio of the two monomers of 1:1, dispersed in 2.44mL of water, and added with a magnet and placed on a magnetic stirrer until a transparent clear solution is formed, so as to obtain a monomer aqueous solution;
(2) 0.00789g of ammonium persulfate is added into the monomer aqueous solution, after uniform stirring, the monomer solution is injected into a glass mold, and the glass mold is placed on a hot table to polymerize for 8 hours at 60 ℃ to obtain the supermolecular hydrogel.
EXAMPLE 2 preparation of supramolecular hydrogel P (AA-co-PDP) (total monomer concentration 45% by mass, monomer mass ratio 1:3)
(1) Weighing 0.333g of (3- (methacrylamido) propyl) dimethyl (3-thiopropyl) ammonium hydroxide inner salt and 1g of acrylic acid according to the mass ratio of the two monomers of 1:3, dispersing in 1.63mL of water, adding the magnetons, placing on a magnetic stirrer, and stirring until a transparent clear solution is formed, thus obtaining a monomer aqueous solution;
(2) 0.00685g of ammonium persulfate is added into the monomer aqueous solution, after uniform stirring, the monomer solution is injected into a glass mold, and the glass mold is placed on a hot table to polymerize for 8 hours at 60 ℃ to obtain the supermolecular hydrogel.
EXAMPLE 3 preparation of supramolecular hydrogel P (AA-co-PDP) (total monomer concentration 45% by mass, monomer mass ratio 1:4)
(1) Weighing 0.25g of (3- (methacrylamido) propyl) dimethyl (3-thiopropyl) ammonium hydroxide inner salt and 1g of acrylic acid according to the mass ratio of the two monomers of 1:4, dispersing in 1.50mL of water, adding the magnetons, placing on a magnetic stirrer, and stirring until a transparent clear solution is formed, thus obtaining a monomer aqueous solution;
(2) 0.00672g of ammonium persulfate is added into the monomer aqueous solution, after uniform stirring, the monomer solution is injected into a glass mold, and the glass mold is placed on a hot table to polymerize for 8 hours at 60 ℃ to obtain the supermolecular hydrogel.
EXAMPLE 4 preparation of supramolecular hydrogel P (AA-co-PDP) (total monomer concentration 45% by mass, monomer mass ratio 1:5)
(1) Weighing 0.2g of (3- (methacrylamido) propyl) dimethyl (3-thiopropyl) ammonium hydroxide inner salt and 1g of acrylic acid according to the mass ratio of the two monomers of 1:5, dispersing in 1.47mL of water, adding the magnetons, placing on a magnetic stirrer, and stirring until a transparent clear solution is formed, thus obtaining a monomer aqueous solution;
(2) Adding 0.0066g ammonium persulfate into the monomer aqueous solution, stirring uniformly, injecting the monomer solution into a glass mold, placing the glass mold on a hot table, and polymerizing at 60 ℃ for 8 hours to obtain the supermolecule hydrogel.
EXAMPLE 5 preparation of supramolecular hydrogel P (AA-co-PDP) (total monomer concentration 45% by mass, monomer mass ratio 1:6)
(1) 0.167g of (3- (methacrylamido) propyl) dimethyl (3-thiopropyl) ammonium hydroxide inner salt and 1g of acrylic acid are weighed according to the mass ratio of the two monomers of 1:6, dispersed in 1.43mL of water, added with magnetons and placed on a magnetic stirrer, and stirred until a transparent clear solution is formed, thus obtaining a monomer aqueous solution;
(2) 0.00659g of ammonium persulfate is added into the monomer aqueous solution, after uniform stirring, the monomer solution is injected into a glass mold, and the glass mold is placed on a hot table to polymerize for 8 hours at 60 ℃ to obtain the supermolecular hydrogel.
Example 6 preparation of supramolecular hydrogel P (AA-co-PDP) (total monomer concentration 45% by mass, monomer mass ratio 1:7)
(1) Weighing 0.143g of (3- (methacrylamido) propyl) dimethyl (3-thiopropyl) ammonium hydroxide inner salt and 1g of acrylic acid according to the mass ratio of the two monomers of 1:7, dispersing in 1.40mL of water, adding the magnetons, placing on a magnetic stirrer, and stirring until a transparent clear solution is formed, thus obtaining a monomer aqueous solution;
(2) Adding 0.0065g ammonium persulfate into the monomer aqueous solution, uniformly stirring, injecting the monomer solution into a glass mold, placing the glass mold on a hot table, and polymerizing at 60 ℃ for 8 hours to obtain the supermolecule hydrogel.
Test example 1 mechanical Property test of supramolecular hydrogels prepared with different monomer ratios
The supramolecular hydrogels obtained in examples 1 to 6 were subjected to mechanical properties testing. The stress strain curve of the supramolecular hydrogel is shown in fig. 1, the breaking strain of the hydrogel ranges from 1200% to 4200%, and the breaking strain of the hydrogel is reduced after the increasing of the mass ratio of (3- (methacrylamidopropyl) dimethyl (3-thiopropyl) ammonium hydroxide inner salt to acrylic acid. The reason for this is that as the acrylic acid content increases, more and more hydrogen bonds are present in the three-dimensional network of the supramolecular hydrogel, the elasticity increases, but when the content is too high, the hydrogel network is too dense, the elastic modulus of the material is too high, and thus the breaking strain is reduced. When the mass ratio of the monomers is 1:5, the supramolecular hydrogel has a maximum strain at break of 4200%, so this ratio is selected for subsequent testing.
EXAMPLE 7 preparation of supramolecular hydrogel P (AA-co-PDP) (monomer mass ratio 1:5, total monomer mass concentration 35%)
(1) 0.2g of (3- (methacrylamido) propyl) dimethyl (3-thiopropyl) ammonium hydroxide inner salt and 1g of acrylic acid solution were weighed in a mass ratio of the two monomers of 1:5, dispersed in 2.33mL of water, so that the total mass concentration of the two polymerizable monomers was 35%. Adding magnetons, placing on a magnetic stirrer, and stirring until a transparent clear solution is formed, thus obtaining a monomer solution;
(2) Adding 0.0065g ammonium persulfate into the monomer aqueous solution, uniformly stirring, injecting the monomer solution into a glass mold, placing the glass mold on a hot table, and polymerizing at 60 ℃ for h to obtain the supermolecule hydrogel.
Example 8 preparation of supramolecular hydrogel P (AA-co-PDP) (monomer mass ratio 1:5, total monomer mass concentration 45%)
(1) 0.2g of (3- (methacrylamido) propyl) dimethyl (3-thiopropyl) ammonium hydroxide inner salt and 1g of acrylic acid solution were weighed in a mass ratio of the two monomers of 1:5, dispersed in 1.47mL of water, so that the total mass concentration of the two polymerizable monomers was 45%. Adding magnetons, placing on a magnetic stirrer, and stirring until a transparent clear solution is formed, thus obtaining a monomer solution;
(2) Adding 0.0065g ammonium persulfate into the monomer aqueous solution, uniformly stirring, injecting the monomer solution into a glass mold, placing the glass mold on a hot table, and polymerizing at 60 ℃ for 8 hours to obtain the supermolecule hydrogel.
EXAMPLE 9 preparation of supramolecular hydrogel P (AA-co-PDP) (monomer mass ratio 1:5, total monomer mass concentration 50%)
(1) 0.2g of (3- (methacrylamido) propyl) dimethyl (3-thiopropyl) ammonium hydroxide inner salt and 1g of acrylic acid solution were weighed in a mass ratio of the two monomers of 1:5, dispersed in 1.2mL of water, so that the total mass concentration of the two polymerizable monomers was 50%. Adding magnetons, placing on a magnetic stirrer, and stirring until a transparent clear solution is formed, thus obtaining a monomer solution;
(2) Adding 0.0065g ammonium persulfate into the monomer aqueous solution, uniformly stirring, injecting the monomer solution into a glass mold, placing the glass mold on a hot table, and polymerizing at 60 ℃ for 8 hours to obtain the supermolecule hydrogel.
EXAMPLE 10 preparation of supramolecular hydrogel P (AA-co-PDP) (monomer mass ratio 1:5, total monomer mass concentration 55%)
(1) 0.2g of (3- (methacrylamido) propyl) dimethyl (3-thiopropyl) ammonium hydroxide inner salt and 1g of acrylic acid solution were weighed in a mass ratio of the two monomers of 1:5, dispersed in 0.98mL of water, so that the total mass concentration of the two polymerizable monomers was 55%. Adding magnetons, placing on a magnetic stirrer, and stirring until a transparent clear solution is formed, thus obtaining a monomer solution;
(2) Adding 0.0065g ammonium persulfate into the monomer aqueous solution, uniformly stirring, injecting the monomer solution into a glass mold, placing the glass mold on a hot table, and polymerizing at 60 ℃ for 8 hours to obtain the supermolecule hydrogel.
Test example 2 mechanical Property test of supramolecular hydrogels with different monomer concentrations
The supramolecular hydrogels obtained in examples 7 to 10 were subjected to mechanical properties testing. The stress strain curve of the supramolecular hydrogel is shown in fig. 2, and the breaking strain of the hydrogel is increased and then decreased with the increase of the concentration of the (3- (methacrylamido) propyl) dimethyl (3-thiopropyl) ammonium hydroxide inner salt and the acrylic acid monomer, and the breaking strain of the supramolecular hydrogel is 4200% at the maximum when the concentration of the monomer is 45%. The reason for this is that as the concentration of monomers increases, the number of hydrogen bonds and physical bonds in the three-dimensional network of supramolecular hydrogels increases, so the strain at break increases, but when the concentration is too great, the hydrogel network is too dense, so the elastic modulus of the material is too great, thus resulting in a decrease in the strain at break.
EXAMPLE 11 preparation of supramolecular hydrogel electrolyte P (AA-co-PDP) (monomer mass ratio 1:5, total monomer mass concentration 45%, liCl solution concentration 0.5M)
The supramolecular hydrogel prepared in example 8 was immersed in 0.5M LiCl solution for 24 hours, and after equilibration, the supramolecular hydrogel electrolyte was obtained.
EXAMPLE 12 preparation of supramolecular hydrogel electrolyte P (AA-co-PDP) (monomer mass ratio 1:5, total monomer mass concentration 45%, liCl solution concentration 1.0M)
The supramolecular hydrogel prepared in example 8 was immersed in 1.0M LiCl solution for 24 hours and allowed to equilibrate to obtain a supramolecular hydrogel electrolyte.
EXAMPLE 13 preparation of supramolecular hydrogel electrolyte P (AA-co-PDP) (monomer Mass ratio 1:5, total monomer mass concentration 45%, liCl solution concentration 1.5M)
The supramolecular hydrogel prepared in example 8 was immersed in 1.5M LiCl solution for 24 hours, and after equilibration, the supramolecular hydrogel electrolyte was obtained.
EXAMPLE 14 preparation of supramolecular hydrogel electrolyte P (AA-co-PDP) (monomer mass ratio 1:5, total monomer mass concentration 45%, liCl solution concentration 2.0M)
The supramolecular hydrogel prepared in example 8 was immersed in 2.0M LiCl solution for 24h, and allowed to equilibrate to the supramolecular hydrogel electrolyte.
EXAMPLE 15 preparation of supramolecular hydrogel electrolyte P (AA-co-PDP) (monomer Mass ratio 1:5, total monomer mass concentration 45%, liCl solution concentration 4.0M)
The supramolecular hydrogel prepared in example 8 was immersed in a 4.0M LiCl solution for 24 hours, and after equilibration, a supramolecular hydrogel electrolyte was obtained.
EXAMPLE 16 preparation of supramolecular hydrogel electrolyte P (AA-co-PDP) (monomer Mass ratio 1:5, total monomer mass concentration 45%, liCl solution concentration 6.0M)
The supramolecular hydrogel prepared in example 8 was immersed in a 6.0M LiCl solution for 24 hours, and after equilibration, a supramolecular hydrogel electrolyte was obtained.
Test example 3 mechanical Property test of supramolecular hydrogel electrolyte prepared by soaking in salt solutions of different concentrations
The supramolecular hydrogel electrolytes prepared in examples 11 to 16 were subjected to mechanical property test. The stress-strain curve of the supramolecular hydrogel electrolyte is shown in fig. 3, the corresponding elastic modulus graph and breaking energy graph are shown in fig. 4 and 5, and the breaking strain of the supramolecular hydrogel electrolyte is firstly increased and then decreased along with the increase of the concentration of lithium chloride salt, and the elastic modulus is firstly decreased and then increased, and the breaking energy is firstly decreased and then increased. The maximum reaches 2880% when the concentration of LiCl is 1.5M. The elastic modulus of the hydrogel increases with the concentration of the salt solution, and after the 6M LiCl solution is soaked, the elastic modulus is 202KPa and 78 times of that of the original hydrogel, because the super-molecular hydrogel is soaked in the salt solution to increase the hydrophobic association, the hydrophobic association is enhanced with the increase of the salt concentration, the breaking strain is reduced, the elastic modulus of the hydrogel electrolyte is gradually increased, and the breaking energy is increased. The supramolecular hydrogel electrolyte soaked with 1.5M saline solution was thus selected for subsequent testing.
Test example 4 ion conductivity test of supramolecular hydrogel electrolytes prepared by soaking different salt concentrations
The supramolecular hydrogel electrolytes prepared in examples 11 to 16 were subjected to ion conductivity test. Ion conductivity of the supramolecular hydrogel electrolyte as shown in fig. 6, it can be seen from the graph that the conductivity of the supramolecular hydrogel electrolyte gradually decreases as the concentration of the lithium chloride salt increases, because the increase of hydrophobic interactions results in a higher energy barrier for chain-to-chain movement, a slower rate of electron transport, and no good adhesion to the electrode, resulting in a gradual decrease in the conductivity of the supramolecular hydrogel electrolyte.
Application example 1 preparation of Flexible super capacitor
The supermolecular hydrogel electrolyte film prepared in example 13 was attached with PEDOT: PSS electrodes on both sides to prepare a flexible supercapacitor.
Test example 5 electrochemical Performance test of Flexible super capacitor
The supercapacitor prepared in application example 1 was tested for a circulating current curve, a constant current charge-discharge curve, and impedance diagrams as shown in fig. 7, 8, and 9. The result shows that the circulating current curve of the super capacitor keeps a rectangular shape at a high scanning rate, the constant current charge-discharge curve of the super capacitor keeps a good triangular shape at different current densities, and the super capacitor has high conductivity of 0.96S/m, so that the super capacitor prepared based on the super molecular hydrogel electrolyte film has excellent electrochemical performance.
Application example 2 preparation of Flexible resistance sensor
Copper wires are connected to two sides of the supermolecule hydrogel electrolyte prepared in the embodiment 13, and VHB adhesive tapes are attached to two sides of the hydrogel electrolyte to be packaged, so that the flexible resistance sensor can be assembled.
Test example 6 stress response of Flexible resistance sensor
The response of the flexible resistive sensor prepared in application example 2 to repeated stress was tested, as shown in fig. 10, and the results showed that the flexible sensor remained stable and sensitive to the same stress.
Test example 7 Strain response of Flexible resistance sensor
The flexible resistance sensor prepared in application example 2 was subjected to stretching and recovery of different magnitudes, and the response of the flexible resistance sensor to different strains was tested, as shown in fig. 11, and the results showed that the flexible sensor remained stable and sensitive to the different strains.
Test example 8 temperature response of Flexible resistance sensor
The flexible resistance sensor prepared in application example 2 was attached to a hot bench to test its stimulus response to temperature, and the flexible sensor was increased from room temperature to 90 ℃ and then cooled to room temperature, and repeated a plurality of times, and the result is shown in fig. 12, and the result shows that the resistance of the flexible sensor is stable and sensitive with temperature.
Test example 9 Strain response of Flexible resistance sensor
The flexible resistance sensor prepared in application example 2 was placed in a tensile instrument to test the response of its resistance to strain, and the result is shown in fig. 13, in which it can be seen that the resistance change gradually increases with increasing strain, whereby the sensitivity factor GF of the flexible resistance sensor can be calculated, and the result is shown in an inset. The result shows that the flexible sensor has high sensitivity of 9.1 (300%).
The foregoing description is only illustrative of the present invention and is not intended to limit the scope of the invention, and all equivalent structures or equivalent processes or direct or indirect application in other related technical fields are included in the scope of the present invention.
Claims (10)
1. The preparation method of the supermolecular hydrogel electrolyte is characterized by comprising the following steps of:
(1) Dissolving (3- (methacrylamido) propyl) dimethyl (3-thiopropyl) ammonium hydroxide inner salt and acrylic acid in water, and uniformly stirring to obtain a monomer aqueous solution;
(2) Adding an initiator into the monomer aqueous solution, and performing polymerization reaction to obtain supermolecule hydrogel;
(3) Soaking the supermolecule hydrogel in the aqueous solution of the salt electrolyte for 24-48 hours to obtain the supermolecule hydrogel electrolyte.
2. The process according to claim 1, wherein in step (1), the total mass concentration of (3- (methacrylamido) propyl) dimethyl (3-thiopropyl) ammonium hydroxide inner salt and acrylic acid in the aqueous monomer solution is from 35% to 55%, preferably 45%.
3. The preparation method according to claim 1, wherein in the step (1), the mass ratio of the (3- (methacrylamido) propyl) dimethyl (3-thiopropyl) ammonium hydroxide inner salt to the acrylic acid in the aqueous monomer solution is 1:1-1:7, preferably 1:5; in the step (3), the concentration of the salt solution is 0.5M to 6M, preferably 1.5M.
4. The method according to claim 1, wherein in the step (1), the stirring process is: stirring at 22-26 deg.c and 200-500 rpm until homogeneous transparent aqueous monomer solution is obtained.
5. The method according to claim 1, wherein in the step (2), the initiator is ammonium persulfate; the mass concentration of the ammonium persulfate is 0.1-0.5%.
6. The method according to claim 1, wherein in the step (2), the polymerization is performed by: after adding an initiator into the monomer aqueous solution, stirring at a rotation speed of 200-500 rpm at 22-26 ℃ until a uniform and transparent solution is obtained, then injecting the solution into a glass mold, and polymerizing at 55-65 ℃ for 5-8 hours to obtain the supermolecule hydrogel.
7. The method according to claim 1, wherein in the step (3), the aqueous salt electrolyte solution is an aqueous solution of potassium chloride, lithium chloride, sodium chloride, potassium sulfate, lithium sulfate or sodium sulfate.
8. The supramolecular hydrogel electrolyte prepared by the preparation method according to any one of claims 1 to 7.
9. The use of the supramolecular hydrogel electrolyte according to claim 8 for the preparation of flexible stretchable supercapacitors, wherein the specific application method is: and (3) attaching PEDOT: PSS electrodes on two sides of the supermolecule hydrogel electrolyte to prepare the flexible stretchable supercapacitor.
10. The use of the supramolecular hydrogel electrolyte according to claim 8 for the preparation of flexible resistive sensors, wherein the specific application method is: copper wires are connected to two sides of the supermolecule hydrogel electrolyte, and VHB adhesive tapes are attached to two sides of the hydrogel electrolyte to complete packaging, so that the flexible resistance sensor is manufactured.
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