CN113012947A - Preparation method and application of water-based solid electrolyte - Google Patents
Preparation method and application of water-based solid electrolyte Download PDFInfo
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Classifications
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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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- 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
- C08F220/52—Amides or imides
- C08F220/54—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide
- C08F220/56—Acrylamide; Methacrylamide
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01B—MEASURING LENGTH, THICKNESS OR SIMILAR LINEAR DIMENSIONS; MEASURING ANGLES; MEASURING AREAS; MEASURING IRREGULARITIES OF SURFACES OR CONTOURS
- G01B7/00—Measuring arrangements characterised by the use of electric or magnetic techniques
- G01B7/16—Measuring arrangements characterised by the use of electric or magnetic techniques for measuring the deformation in a solid, e.g. by resistance strain gauge
- G01B7/18—Measuring arrangements characterised by the use of electric or magnetic techniques for measuring the deformation in a solid, e.g. by resistance strain gauge using change in resistance
-
- 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
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- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Power Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Manufacturing & Machinery (AREA)
- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
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Abstract
The application discloses a preparation method and application of a water system solid electrolyte, wherein the method comprises the following steps: carrying out photoinitiation reaction on materials containing a substance E, a metal chloride, an organic solvent, a cross-linking agent, an acrylamide compound, an acrylic acid compound and a photoinitiator to obtain the water-based solid electrolyte; the substance E is at least one selected from polyvinyl alcohol, gelatin, chitosan and agar. The high-voltage multifunctional aqueous solid electrolyte with long-term stability prepared by the invention can be stored at room temperature for a long time without any protection packaging measures, the quality and the appearance of the electrolyte are almost kept unchanged, and the water absorption can reach dynamic balance.
Description
Technical Field
The application relates to a preparation method and application of a water system solid electrolyte, belonging to the technical field of preparation of high polymer materials.
Background
With the advent of the 5G era, flexible wearable devices, printable smart materials and electronic skins are widely applied. The flexible sensor is an essential component for signal acquisition at the front end of a related flexible optoelectronic device, and the flexible super capacitor is one of important energy supply components for supporting the related flexible optoelectronic device to normally work. The conductive hydrogel solid electrolyte organically combines a hydrophilic matrix and a conductive medium, is a functional material with good processability, biocompatibility, high flexibility and excellent electrochemical performance, can be used as a flexible functional element, and helps electronic devices develop towards flexibility and diversification. Therefore, the preparation of the multifunctional gel-based energy storage device and the multifunctional gel-based sensing device has great feasibility and research significance. However, the hydrogel electrolyte is easy to lose water during storage, so that the mechanical property and the conductivity of the hydrogel electrolyte are affected, and besides, a super capacitor assembled by the water-based electrolyte has low withstand voltage and cannot provide high power density, and the factors greatly limit the application of the conductive hydrogel electrolyte in the fields of energy storage and sensing. Therefore, the preparation of the water-based solid electrolyte which is stable for a long time and resistant to high pressure has higher challenge and application value.
A great deal of research has been done to obtain an aqueous solid electrolyte that is stable for a long period of time. However, there has been still little progress in the construction of an aqueous electrolyte having both long-term stability and an ultrahigh withstand voltage. Researchers often improve the stability of the water-based electrolyte by adding organic small-molecule polyol with low condensation point and high boiling point, but the conductivity of the material is reduced, excessive organic solvent is easily separated out, the stability of the material is damaged, and the dynamic balance of the gel electrolyte with lost water is difficult. Meanwhile, although the voltage window of the aqueous electrolyte is improved to a certain extent by adding the organic solvent, the distance from the aqueous electrolyte for preparing the ultrahigh voltage still has a certain gap. In addition, the preparation of multifunctional water-based solid electrolytes with both energy storage and multi-module sensing functions still has great challenges.
Disclosure of Invention
In order to solve the defects of the prior art, the invention provides a preparation method of a high-voltage multifunctional water-based solid electrolyte which is stable for a long time. The polymer/polyacrylamide compound-acrylic acid compound double-network hydrogel solid electrolyte is constructed aiming at the problems of poor long-term stability and low withstand voltage of the existing water system solid electrolyte, difficult preparation of the multifunctional solid electrolyte and the like, and an organic solvent and a metal chloride are introduced into a system to synergistically improve the stability and the withstand voltage of the electrolyte. The construction of the high molecular polymer/polyacrylamide compound-acrylic acid compound double-network hydrogel electrolyte can improve the water locking capacity of the material and the stability of the electrolyte on one hand, and provides better mechanical cycle performance on the other hand, which has a greater effect on the cycle stability of the strain sensor. The addition of the organic solvent improves the long-term stability of the aqueous electrolyte on one hand and improves the voltage window of the electrolyte on the other hand. The metal chloride not only provides conductivity, but also can cooperate with the organic solvent to regulate and control the dynamic balance of water absorption of the electrolyte due to better water absorption capacity, so as to achieve the effect of long-term stability, and in addition, the metal chloride can also achieve the effect of increasing the voltage window through the interaction with water molecules. The water system solid electrolyte prepared by the invention can be stored for a long time at room temperature, and can achieve the dynamic balance of lost water. The long-term stable high-voltage multifunctional aqueous solid electrolyte as a flexible wearable super capacitor electrode shows an ultrahigh voltage window and an excellent capacity retention rate, and as a strain sensor electrode, the high-voltage multifunctional aqueous solid electrolyte shows a higher sensitivity factor and cycle stability.
The preparation method of the aqueous solid electrolyte comprises the following steps: firstly, preparing a substance E aqueous solution with a certain concentration, then adding an organic solvent and a metal chloride, stirring and mixing to obtain a substance E/organic solvent/metal chloride solution, then adding an acrylamide compound, an acrylic compound, a cross-linking agent and an initiator to obtain a substance E/organic solvent/metal chloride/acrylamide compound/acrylic compound mixed solution, finally injecting the precursor solution into a mold, and carrying out photoinitiation under ultraviolet light to obtain the long-term stable high-pressure multifunctional aqueous solid electrolyte. The high-voltage multifunctional aqueous solid electrolyte with long-term stability prepared by the invention can be stored at room temperature for a long time without any protection packaging measures, the quality and the appearance of the electrolyte are almost kept unchanged, and the water absorption can reach dynamic balance. In addition, the long-term stable high-voltage multifunctional aqueous solid electrolyte can be applied to multiple fields of flexible wearable energy storage equipment, sensing devices and the like, shows an ultrahigh voltage window and an excellent capacity retention rate as a flexible wearable supercapacitor electrode, and shows a higher sensitivity factor and cycle stability as a strain sensor electrode.
According to a first aspect of the present application, there is provided a method of producing an aqueous solid electrolyte, the method comprising:
carrying out photoinitiation reaction on materials containing a substance E, a metal chloride, an organic solvent, a cross-linking agent, an acrylamide compound, an acrylic acid compound and a photoinitiator to obtain the water-based solid electrolyte;
the substance E is at least one selected from polyvinyl alcohol, gelatin, chitosan and agar.
Optionally, the metal chloride is selected from at least one of calcium chloride, lithium chloride, aluminum chloride, and sodium chloride.
Optionally, the crosslinker is selected from N, N' -methylenebisacrylamide.
Optionally, the acrylamide compound is selected from at least one of acrylamide, methacrylamide, N-isopropylacrylamide and dimethylacrylamide.
Optionally, the acrylic compound is selected from at least one of acrylic acid, methacrylic acid, and diacrylic acid.
Optionally, the organic solvent is selected from at least one of glycerol, ethylene glycol, and dimethyl sulfoxide.
Optionally, the photoinitiator is selected from at least one of photoinitiator 2959, photoinitiator 1173, photoinitiator MBF.
Optionally, the conditions of the photoinitiated reaction are: the wavelength of light is 340-380 nm; the distance between the material and the light source is 20 cm-90 cm; the illumination time is 0.5-2 h.
Optionally, the photoinitiated reaction is performed under ultraviolet light irradiation.
Optionally, the method comprises:
(1) obtaining a solution A containing a substance E, water and an organic solvent;
(2) and carrying out photoinitiation reaction on a mixture containing the solution A, the metal chloride, the acrylamide compound, the acrylic compound, the cross-linking agent and the photoinitiator to obtain the water-based solid electrolyte.
Preferably, the organic solvent is at least one selected from glycerol, ethylene glycol and dimethyl sulfoxide.
Optionally, the method comprises:
(a) obtaining an aqueous solution containing substance E;
(b) mixing the aqueous solution containing the substance E obtained in the step (a) with an organic solvent to obtain the solution A;
(c) mixing the solution A and metal chloride to obtain a solution B;
(d) and carrying out photoinitiation reaction on the mixture containing the solution B, the acrylamide compound, the acrylic compound, the cross-linking agent and the photoinitiator to obtain the water-based solid electrolyte.
Optionally, in the step (a), the mass content of the substance E in the aqueous solution is 0.5-10 wt%.
Alternatively, in said step (a), the mass content of substance E in the aqueous solution has an upper limit independently selected from 5 wt%, 4 wt%, 3 wt%, 2 wt%, 1 wt%, and a lower limit independently selected from 0.5 wt%, 4 wt%, 3 wt%, 2 wt%, 1 wt%.
Optionally, the step (d) comprises: and injecting a mixture containing the solution B, the acrylamide compound, the acrylic compound, the cross-linking agent and the photoinitiator into a mold, and carrying out photoinitiation reaction under ultraviolet light to obtain the water-based solid electrolyte.
Optionally, in the step (b), the amount of the organic solvent added is 40-160% of the mass of water in the aqueous solution containing the substance E.
Optionally, in step (b), the organic solvent is added in an amount such that the upper limit of the mass of water in the aqueous solution containing substance E is independently selected from 160%, 130%, 110%, 90%, 70%, 50%, and the lower limit is independently selected from 40%, 130%, 110%, 90%, 70%, 50%.
Optionally, in the step (c), the addition amount of the calcium chloride is 1-15% of the total mass of the water and the organic solvent in the aqueous solution containing the substance E.
Optionally, in step (c), the calcium chloride is added in an amount such that the upper limit of the total mass of water and the organic solvent in the aqueous solution containing the substance E is independently selected from 15%, 13%, 11%, 9%, 7%, 5%, 3%, and the lower limit is independently selected from 1%, 13%, 11%, 9%, 7%, 5%, 3%.
Optionally, in the step (d), the addition amount of the acrylamide compound is 8-15 times of the mass of the substance E in the solution B;
the adding amount of the acrylic compound is 50-110% of the mass of the substance E in the solution B;
the addition amount of the cross-linking agent is 0.04-0.08% of the total mass of the acrylamide compound and the acrylic acid compound;
the addition amount of the photoinitiator is 2-4% of the total mass of the acrylamide compound and the acrylic acid compound.
Alternatively, in the step (d), the acrylamide-based compound is added in an amount that the upper limit of the mass of the substance E in the solution B is independently selected from 15 times, 13 times and 11 times, and the lower limit thereof is independently selected from 8 times, 13 times and 11 times.
Optionally, the acrylic compound is added in an amount such that the upper limit and the lower limit of the mass of substance E in the solution B are independently selected from 110%, 90%, 70%, and 60%, respectively, and independently selected from 50%, 90%, 70%, and 60%, respectively.
Optionally, the cross-linking agent is added in an amount such that the upper limit of the total mass of the acrylamide-based compound and the acrylic compound is independently selected from 0.08%, 0.07%, 0.06%, and the lower limit is independently selected from 0.04%, 0.07%, 0.06%.
Alternatively, the method of preparing the aqueous solid electrolyte includes:
1) adding the substance E into deionized water, heating and dissolving for 1-2 hours in a water bath at 80-95 ℃ to obtain a substance E water solution with the concentration of 0.5-5 wt%;
2) adding a certain amount of organic solvent into the substance E aqueous solution obtained in the step 1), and continuously heating for 1-1.5 hours to obtain a substance E/organic solvent solution, wherein the adding amount of the organic solvent is 40-160% of the weight of the deionized water used in the step 1);
3) adding a certain amount of metal chloride into the substance E/organic solvent solution obtained in the step 2), heating and stirring for 5-15 minutes to obtain a substance E/organic solvent/metal chloride composite solution, wherein the adding amount of the metal chloride is 1% -15% of the total weight of the deionized water and the organic solvent;
4) sequentially adding an acrylamide compound, an acrylic acid compound, a cross-linking agent and a photoinitiator into the substance E/organic solvent/metal chloride compound solution obtained in the step 3), and uniformly stirring to obtain a substance E/organic solvent/metal chloride/acrylamide compound/acrylic acid compound solution; the addition amount of the acrylamide compound is 8-15 times of the weight of the substance E, the addition amount of the acrylic compound is 50-110% of the weight of the substance E, the addition amount of the cross-linking agent is 0.04-0.08% of the total weight of the acrylamide compound and the acrylic compound, and the addition amount of the photoinitiator is 2-4% of the total weight of the acrylamide compound and the acrylic compound.
5) Injecting the substance E/organic solvent/metal chloride/acrylamide compound/acrylic acid compound composite solution obtained in the step 4) into a mold, and carrying out photoinitiation reaction under an ultraviolet lamp to obtain a long-term stable high-pressure multifunctional aqueous solid electrolyte; wherein the wavelength of the photoinitiated reaction is 365nm, the distance between a light source and the die is 20 cm-90 cm, and the illumination time is 0.5-2 h.
In particular, the long-term stability of the long-term stable high-voltage multifunctional aqueous solid electrolyte in the present application is shown in that it can be stored at room temperature for a long period of time, and water absorption can reach a dynamic balance, showing excellent stability.
In particular, the high voltage of the long-term stable high-voltage multifunctional aqueous solid electrolyte in the present application is expressed as an electrolyte of a supercapacitor, can withstand a voltage window of 2.5V, and exhibits excellent cycle stability.
In particular, the versatility of the long-term stable high-voltage multifunctional aqueous solid electrolyte in the present application is manifested in a number of application fields where it can be used as a solid electrolyte for flexible stretchable supercapacitors and electrodes for strain sensors.
According to a second aspect of the present application, there is provided an aqueous solid electrolyte selected from at least one of the aqueous solid electrolytes prepared according to the above-described methods.
Optionally, the water-based solid electrolyte is a double-network hydrogel solid electrolyte, wherein the first network is a physical cross-linked network formed by the substance E, the second network is a network formed by chemically cross-linking an acrylamide compound and an acrylic acid compound, and the two networks penetrate and are entangled to form the double-network hydrogel solid electrolyte with strong interaction.
Optionally, the tensile strength of the aqueous solid electrolyte is 0.15 to 0.35 Mpa; the elongation at break is 900-1500%.
According to a final aspect of the application, an aqueous solid electrolyte prepared according to the above method, and the use of at least one of the above aqueous solid electrolytes in strain sensors, flexible supercapacitors are provided.
The beneficial effects that this application can produce include:
(1) substance E in the present application has good biocompatibility and biodegradability. The hydrogel prepared by using the substance E as a raw material can be used in the biotechnology fields of biological tissue engineering, drug controlled release and the like.
(2) The water system electrolyte prepared by the method has excellent stability, can be stored at room temperature for a long time without any protection packaging measures, the quality and the appearance of the electrolyte are almost kept unchanged, and the loss of rehydration can reach dynamic balance.
(3) The aqueous electrolyte prepared by the method has ultrahigh withstand voltage, has a voltage window of 2.5V as the electrolyte of a super capacitor, and has great significance for expanding the application of the aqueous electrolyte.
(4) The aqueous electrolyte prepared by the method fully exerts the synergistic effect of the organic solvent and the salt, not only has better stability and ultrahigh withstand voltage, but also has high conductivity and mechanical property.
(5) The high-voltage multifunctional aqueous solid electrolyte prepared by the method can be applied to the fields of flexible super capacitors and sensors. The prepared sensor and the super capacitor have good stability, the influence of the placing time on the sensitivity of the sensor and the capacity of the super capacitor is small, and the sensor and the super capacitor have great practical application potential.
(6) The flexible all-solid-state supercapacitor prepared based on the water system solid electrolyte still keeps higher capacity retention rate after bending and stretching experiments, and the prepared strain sensor has higher sensitive factor and wide application range and can be directly used for human body detection and specific rehabilitation training.
Drawings
FIG. 1 is a schematic view of an aqueous solid electrolyte obtained in example 1;
FIG. 2 is a stress-strain curve of the aqueous solid electrolyte obtained in example 1;
FIG. 3 is a water retention test chart of the aqueous solid electrolyte obtained in example 1;
FIG. 4 is a charge and discharge curve of the assembled all-solid-state flexible supercapacitor of example 3;
FIG. 5 shows the specific capacity of the assembled all-solid-state flexible supercapacitor of example 3 at different current densities;
fig. 6 is a graph of the resistance change of the flexible strain sensor prepared in example 4 at different tensile lengths.
Fig. 7 is a cyclic voltammogram of the aqueous solid electrolyte obtained in example 3 after stretching.
Detailed Description
The raw materials in the examples of the present application were all purchased commercially, unless otherwise specified.
The mechanical properties of the film material were measured by means of a general tensile tester (MTS CMT4104) equipped with a 1kN force sensor, at a tensile speed of 100mm min-1。
The dynamic electrical and mechanical response signals were recorded by a universal materials tester and a digital source meter (Keithley 2450 by Tektronix, usa), respectively.
The application provides a long-term stable high-voltage multifunctional aqueous solid electrolyte and a specific preparation method thereof, wherein the specific preparation method comprises the following steps:
the specific preparation method comprises the following steps:
1) adding the substance E into deionized water, heating and dissolving for 1-2 hours in a water bath at 80-95 ℃ to obtain a substance E water solution with the concentration of 0.5-5 wt%;
2) adding a certain amount of organic solvent into the substance E aqueous solution obtained in the step 1), and continuously heating for 1-1.5 hours to obtain a substance E/organic solvent solution, wherein the adding amount of the organic solvent is 40-150% of the weight of the deionized water used in the step 1);
3) adding a certain amount of metal chloride into the substance E/organic solvent solution obtained in the step 2), heating and stirring for 5-15 minutes to obtain a substance E/organic solvent/metal chloride composite solution, wherein the adding amount of the metal chloride is 1% -15% of the total weight of the deionized water and the organic solvent;
4) in the substance E/organic solvent/metal chloride composite solution obtained in the step 3), sequentially stirring an acrylamide compound, an acrylic acid compound, a cross-linking agent and a photoinitiator uniformly to obtain a substance E/organic solvent/metal chloride/acrylamide compound/acrylic acid compound composite solution; the addition amount of the acrylamide compound is 10-15 times of the weight of the substance E, the addition amount of the acrylic compound is 50-110% of the weight of the substance E, the addition amount of the cross-linking agent is 0.05-0.08% of the total weight of the acrylamide compound and the acrylic compound, and the addition amount of the photoinitiator is 2-4% of the total weight of the acrylamide compound and the acrylic compound.
5) Injecting the substance E/organic solvent/metal chloride/acrylamide compound/acrylic acid compound composite solution obtained in the step 4) into a mold, and carrying out photoinitiation reaction under an ultraviolet lamp to obtain a long-term stable high-pressure multifunctional aqueous solid electrolyte; wherein the wavelength of the photoinitiated reaction is 365nm, the distance between a light source and the die is 20 cm-90 cm, and the illumination time is 0.5-2 h.
Example 1
0.3g of polyvinyl alcohol was taken, wherein the degree of polymerization of the polyvinyl alcohol was 1799 and the degree of alcoholysis was 99%. Adding the mixture into 5ml of deionized water, heating and stirring the mixture at 80 ℃ to dissolve the mixture to obtain a polyvinyl alcohol aqueous solution. Adding 7.95g of glycerol into the polyvinyl alcohol aqueous solution, continuously heating and stirring for 1.5 hours to obtain a polyvinyl alcohol/glycerol solution, then adding 0.9g of calcium chloride into the mixed solution, stirring for 10 minutes to obtain a polyvinyl alcohol/glycerol/calcium chloride composite solution, continuously adding 2.5g of acrylamide, 0.16g of acrylic acid, 1.3mg of N, N' -methylene bisacrylamide and 0.06g of Irgacure 2959, and heating and dissolving to obtain a uniform polyvinyl alcohol/glycerol/calcium chloride/acrylamide/acrylic acid composite solution. And ultrasonically defoaming the obtained composite solution, and then introducing the composite solution into a forming mold, wherein the mold is formed by placing a silica gel gasket with the thickness of 2.0mm between two glass sheets. The mold is placed under an ultraviolet lamp for 20cm, and the initiation is carried out for 1.5h under 350nm ultraviolet light (power of 8W), so that the high-pressure multifunctional water system solid electrolyte with long-term stability is obtained, as shown in figure 1, the gel electrolyte has better flexibility, and does not crack under the condition that the strain reaches 400%.
Tensile properties of the aqueous solid electrolyte were tested as follows: the tensile test was carried out on a universal material testing machine using test specimens having a length of 50mm, a width of 5mm and a tensile rate of 50 mm/min. Fig. 2 is a stress-strain curve of the obtained aqueous solid electrolyte, and the obtained test results are: the tensile strength is 0.254MPa, the elongation at break is 1490%, and the electrolyte has better mechanical properties.
Stability test of aqueous solid electrolyte: and weighing the obtained gel sample, placing the gel sample at room temperature, measuring the mass of the gel sample in different time periods, and calculating the water retention rate of the gel sample. Fig. 3 is a water retention rate test chart of the obtained aqueous solid electrolyte, the mass of the electrolyte is maintained above 90% after the electrolyte is stored for 30 days at room temperature, the electrolyte mass and the appearance are almost maintained unchanged, and the water absorption can reach dynamic balance.
Example 2
0.3g of gelatin is added into 4ml of deionized water, and heated and stirred at 80 ℃ to be dissolved to obtain a polyvinyl alcohol aqueous solution. Adding 4g of ethylene glycol into the gelatin aqueous solution, continuously heating and stirring for 1.5 hours to obtain a gelatin/ethylene glycol solution, then adding 0.7g of calcium chloride into the mixed solution, stirring for 10 minutes to obtain a gelatin/ethylene glycol/calcium chloride composite solution, continuously adding 2g of acrylamide, 0.16g of olefine acid, 1.3mg of N, N' -methylenebisacrylamide and 0.064g of Irgacure 2959, and heating and dissolving to obtain a uniform gelatin/ethylene glycol/calcium chloride/acrylamide/acrylic acid composite solution. And ultrasonically defoaming the obtained composite solution, and then introducing the composite solution into a forming mold, wherein the mold is formed by placing a silica gel gasket with the thickness of 2.0mm between two glass sheets. And (3) placing the mould under an ultraviolet lamp for 90cm, and initiating for 1.5h under 365nm ultraviolet light (power of 8W) to obtain the long-term stable high-pressure multifunctional water system solid electrolyte.
Example 3
0.3g of polyvinyl alcohol is taken and added into 5ml of deionized water, and the mixture is heated, stirred and dissolved at 80 ℃ to obtain a polyvinyl alcohol aqueous solution. Adding 4g of dimethyl sulfoxide into a polyvinyl alcohol aqueous solution, continuously heating and stirring for 1.5 hours to obtain a polyvinyl alcohol/dimethyl sulfoxide solution, then adding 0.9g of calcium chloride into the mixed solution, stirring for 10 minutes to obtain a polyvinyl alcohol/dimethyl sulfoxide/calcium chloride composite solution, continuously adding 2.5g of acrylamide, 0.16g of acrylic acid, 1.3mg of N, N' -methylene bisacrylamide and 0.06g of Irgacure 2959, and heating and dissolving to obtain a uniform polyvinyl alcohol/dimethyl sulfoxide/calcium chloride/acrylamide/acrylic acid composite solution. And ultrasonically defoaming the obtained composite solution, and then introducing the composite solution into a forming mold, wherein the mold is formed by placing a silica gel gasket with the thickness of 2.0mm between two glass sheets. And (3) placing the mould under an ultraviolet lamp for 40cm, and initiating for 1.5h under 340nm ultraviolet light (power of 8W) to obtain the long-term stable high-pressure multifunctional water system solid electrolyte.
Cutting the obtained water system solid electrolyte into samples with the length of 10mm, the width of 10mm and the width of 2mm, assembling the samples in a mode of an electrode-gel electrolyte-electrode three-layer structure, and attaching ITO/PET serving as a current collector on a carbon nano tube membrane electrode by using silver paste to prepare the flexible solid super capacitor. Fig. 4 is a charge-discharge curve of the assembled all-solid-state flexible supercapacitor, and it can be seen that the voltage window of the aqueous electrolyte is 2.5V, which achieves the purpose of ultrahigh voltage of the aqueous electrolyte. FIG. 5 shows the specific capacity of the assembled all-solid-state flexible supercapacitor at different current densities, which can be seen at 2mA/cm2At a current density of 94.1mF/cm2The capacitor achieves a higher capacity.
The obtained water system solid electrolyte is cut into a sample with the length of 30mm, the width of 10mm and the width of 2mm, then conductive carbon nano tubes are sprayed, ITO/PET is used as a current collector, and silver slurry is attached to the carbon nano tube membrane electrode to manufacture the flexible solid super capacitor. Fig. 7 is a plot of the current-voltage characteristics of the assembled all-solid-state flexible supercapacitor after undergoing uniaxial stretching at 100% stretching, and it can be seen that the aqueous electrolyte still maintains good electrochemical properties in a stretched and deformed state.
Example 4
0.2g of polyvinyl alcohol is taken and added into 5ml of deionized water, and the mixture is heated, stirred and dissolved at 80 ℃ to obtain a polyvinyl alcohol aqueous solution. Adding 4g of dimethyl sulfoxide into a polyvinyl alcohol aqueous solution, continuously heating and stirring for 1.5 hours to obtain a polyvinyl alcohol/dimethyl sulfoxide solution, then adding 1.38g of calcium chloride into the mixed solution, stirring for 10 minutes to obtain a polyvinyl alcohol/dimethyl sulfoxide/calcium chloride composite solution, continuously adding 2.5g of acrylamide, 0.16 part of acrylic acid, 1.3mg of N, N' -methylene bisacrylamide and 0.064g of Irgacure 2959, and heating and dissolving to obtain a uniform polyvinyl alcohol/dimethyl sulfoxide/calcium chloride/acrylamide/acrylic acid composite solution. And ultrasonically defoaming the obtained composite solution, and then introducing the composite solution into a forming mold, wherein the mold is formed by placing a silica gel gasket with the thickness of 2.0mm between two glass sheets. And (3) placing the mould under an ultraviolet lamp for 40cm, and initiating for 1.5h under 350nm ultraviolet light (power of 8W) to obtain the long-term stable high-pressure multifunctional water system solid electrolyte. The hydrogel sample is made into a strip shape with the length of 50mm, the width of 5mm and the thickness of 2mm, an ITO/PET film connecting lead is adhered to two sides of a gel electrolyte, the ITO/PET film is in closer contact with the gel electrolyte through conductive silver paste, and a flexible strain sensor is prepared and tested. Fig. 6 is a resistance change curve of the flexible strain sensor under different stretching lengths, and it can be seen that the sensor has better resistance response in a wide strain range, and the sensitivity factor reaches 5, which indicates that the long-term stable high-pressure multifunctional water-based solid electrolyte has greater application potential in the field of strain sensors.
Example 5
0.3g of chitosan is added into 5ml of deionized water, and the chitosan solution is obtained by heating, stirring and dissolving at 80 ℃. Adding 7.95g of glycerol into the chitosan aqueous solution, continuously heating and stirring for 1.5 hours to obtain a chitosan/glycerol solution, then adding 0.9g of aluminum chloride into the mixed solution, stirring for 10 minutes to obtain a chitosan/glycerol/aluminum chloride composite solution, continuously adding 2.5g of acrylamide, 0.16g of acrylic acid, 1.3mg of N, N' -methylene bisacrylamide and 0.06g of Irgacure 2959, and heating and dissolving to obtain a uniform chitosan/glycerol/aluminum chloride/acrylamide/acrylic acid composite solution. And ultrasonically defoaming the obtained composite solution, and then introducing the composite solution into a forming mold, wherein the mold is formed by placing a silica gel gasket with the thickness of 2.0mm between two glass sheets. And (3) placing the mould under an ultraviolet lamp for 20cm, and initiating for 1.5h under 350nm ultraviolet light (power of 8W) to obtain the long-term stable high-pressure multifunctional water system solid electrolyte.
Example 6
0.3g of agar is added into 5ml of deionized water, and heated and stirred at 60 ℃ to be dissolved to obtain an agar aqueous solution. Adding 7.95g of glycerol into the agar aqueous solution, continuously heating and stirring for 1.5 hours to obtain an agar/glycerol solution, adding 0.9g of lithium chloride into the mixed solution, stirring for 10 minutes to obtain an agar/glycerol/lithium chloride composite solution, continuously adding 2.5g of acrylamide, 0.16g of acrylic acid, 1.3mg of N, N' -methylenebisacrylamide and 0.06g of Irgacure 2959, and heating and dissolving to obtain a uniform agar/glycerol/lithium chloride/acrylamide/acrylic acid composite solution. And ultrasonically defoaming the obtained composite solution, and then introducing the composite solution into a forming mold, wherein the mold is formed by placing a silica gel gasket with the thickness of 2.0mm between two glass sheets. And (3) placing the mould under an ultraviolet lamp for 20cm, and initiating for 1.5h under 350nm ultraviolet light (power of 8W) to obtain the long-term stable high-pressure multifunctional water system solid electrolyte.
Although the present application has been described with reference to a few embodiments, it should be understood that various changes, substitutions and alterations can be made herein without departing from the spirit and scope of the application as defined by the appended claims.
Claims (10)
1. A method of preparing an aqueous solid electrolyte, the method comprising:
carrying out photoinitiation reaction on materials containing a substance E, a metal chloride, an organic solvent, a cross-linking agent, an acrylamide compound, an acrylic acid compound and a photoinitiator to obtain the water-based solid electrolyte;
the substance E is at least one selected from polyvinyl alcohol, gelatin, chitosan and agar.
2. The production method according to claim 1, wherein the metal chloride is at least one selected from the group consisting of calcium chloride, lithium chloride, aluminum chloride, and sodium chloride;
the cross-linking agent is selected from N, N' -methylene bisacrylamide;
the acrylamide compound is selected from at least one of acrylamide, methacrylamide, N-isopropyl acrylamide and dimethylacrylamide;
the acrylic compound is at least one of acrylic acid, methacrylic acid and diacrylic acid;
the organic solvent is at least one of glycerol, glycol and dimethyl sulfoxide;
the photoinitiator is selected from at least one of a photoinitiator 2959, a photoinitiator 1173 and a photoinitiator MBF.
3. The method of claim 1, wherein the conditions of the photoinitiated reaction are as follows: the wavelength of light is 340-380 m; the distance between the material and the light source is 20 cm-90 cm; the illumination time is 0.5-2 h.
4. The method of claim 1, wherein the photoinitiated reaction is carried out under ultraviolet light irradiation.
5. The method of manufacturing according to claim 1, comprising:
(1) obtaining a solution A containing a substance E, water and an organic solvent;
(2) and carrying out photoinitiation reaction on a mixture containing the solution A, the metal chloride, the acrylamide compound, the acrylic compound, the cross-linking agent and the photoinitiator to obtain the water-based solid electrolyte.
6. The method of manufacturing according to claim 5, comprising:
(a) obtaining an aqueous solution containing substance E;
(b) mixing the aqueous solution containing the substance E obtained in the step (a) with an organic solvent to obtain the solution A;
(c) mixing the solution A and metal chloride to obtain a solution B;
(d) and carrying out photoinitiation reaction on the mixture containing the solution B, the acrylamide compound, the acrylic compound, the cross-linking agent and the photoinitiator to obtain the water-based solid electrolyte.
7. The preparation method according to claim 6, wherein in the step (a), the mass content of the substance E in the aqueous solution is 0.5-10 wt%;
preferably, in the step (b), the adding amount of the organic solvent is 40-160% of the mass of water in the aqueous solution containing the substance E;
preferably, in the step (c), the adding amount of the metal chloride is 1-15% of the total mass of water and the organic solvent in the aqueous solution containing the substance E;
preferably, in the step (d), the addition amount of the acrylamide compound is 8-15 times of the mass of the substance E in the solution B;
the adding amount of the acrylic compound is 50-110% of the mass of the substance E in the solution B;
the addition amount of the cross-linking agent is 0.04-0.08% of the total mass of the acrylamide compound and the acrylic acid compound;
the addition amount of the photoinitiator is 2-4% of the total mass of the acrylamide compound and the acrylic acid compound.
8. An aqueous solid electrolyte characterized in that it is at least one selected from the aqueous solid electrolytes produced by the method according to any one of claims 1 to 7.
9. The aqueous solid electrolyte according to claim 8, characterized in that the aqueous solid electrolyte is a double-network hydrogel solid electrolyte;
preferably, the tensile strength of the aqueous solid electrolyte is 0.15 to 0.35 Mpa; the elongation at break is 900-1500%.
10. Use of at least one of the aqueous solid electrolyte prepared according to the method of any one of claims 1 to 7, the aqueous solid electrolyte of claim 8 or 9 in a strain sensor, a flexible supercapacitor.
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