CN109810225B - Crystalline composite gel electrolyte and preparation method and application thereof - Google Patents

Crystalline composite gel electrolyte and preparation method and application thereof Download PDF

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CN109810225B
CN109810225B CN201910190477.3A CN201910190477A CN109810225B CN 109810225 B CN109810225 B CN 109810225B CN 201910190477 A CN201910190477 A CN 201910190477A CN 109810225 B CN109810225 B CN 109810225B
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gel electrolyte
composite gel
electrolyte
soluble salt
sodium acetate
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CN109810225A (en
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魏俊杰
王启刚
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Tongji University
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    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/13—Energy storage using capacitors

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Abstract

The invention relates to a preparation method and application of a crystalline composite gel electrolyte, which is characterized by comprising the following steps: (1) adding the gelling component and soluble salt into water, and stirring until the gelling component and the soluble salt are completely dissolved to form a transparent and uniform solution, so as to obtain a gel precursor solution; (2) gelling the gel precursor solution obtained in the step (1) to prepare hydrogel containing saturated soluble salt; (3) and (3) placing a seed crystal above the hydrogel prepared in the step (2) to obtain the crystalline composite gel electrolyte. Compared with the prior art, the preparation process is simple and efficient, the materials are cheap and easy to obtain, the prepared composite gel electrolyte has higher mechanical strength and ionic conductivity, can be applied to energy storage devices such as super capacitors and the like, can automatically adjust the temperature of the materials for different environmental temperatures, can maintain the temperature stability of a system in a short time even in extreme environments, and has important significance in coping with disasters such as fire and the like.

Description

Crystalline composite gel electrolyte and preparation method and application thereof
Technical Field
The invention relates to a gel material, in particular to a crystalline composite gel electrolyte and preparation and application thereof.
Background
The increasing demand for energy sources places higher demands on the development of energy storage devices. Common electrochemical energy storage devices include lithium ion batteries, supercapacitors, solar cells, etc., and the performance of these energy storage devices is mainly determined by their electrode materials and electrolyte materials. The electrolyte may be classified into a liquid electrolyte and a solid electrolyte according to the presence of the electrolyte. The liquid electrolyte is easy to leak during use due to the fluidity, so that the danger of combustion and even explosion is caused, and the solid electrolyte solves the problem and simultaneously leads the packaging process of the device to be relatively simpler.
The gel electrolyte is a solid electrolyte which is widely researched, has the characteristics of high liquid content and fixed form, and has some advantages of liquid electrolytes and other solid electrolytes. Compared with a liquid electrolyte, the gel electrolyte can effectively solve the problems of liquid leakage and packaging of the energy storage device due to the solid property of the gel electrolyte; compared with ceramic solid electrolyte, the electrolyte greatly improves the ionic conductivity of the electrolyte and improves the electrochemical performance of the solid energy storage device due to high liquid content of the electrolyte.
In addition to the advantages described above, gel electrolytes also have some unique advantages. Due to the semi-solid property of the gel electrolyte, most of the gel electrolyte has excellent flexibility and can bear bending, winding and even folding, and the like, and the flexible energy storage device can be prepared by combining the flexible electrode material, so that the gel electrolyte has great application value in the field of wearable equipment. In addition, the flexibility and certain cohesiveness of the gel electrolyte can effectively improve the contact between the gel electrolyte and an electrode material, reduce the contact resistance of a device and improve the overall performance.
However, gel electrolytes also have some problems, the most important of which is the contradiction between mechanical properties and ionic conductivity. Although the gel electrolyte is solid, the mechanical strength of the gel electrolyte is not high, and particularly, the compression modulus of the water-based gel electrolyte is usually only a few kilopascals to a dozen kilopascals, so that the gel electrolyte is far from resisting mechanical damage, when a device is damaged by external force, the risk of damage and even explosion of the device still exists, and the safety requirement is difficult to meet. The mechanical strength of the gel electrolyte is improved by increasing the solid content or adding inorganic fillers, which can cause the great reduction of the ionic conductivity of the gel electrolyte and damage the electrochemical performance of the device.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide a disaster-prevention composite gel electrolyte and a preparation method and application thereof.
The purpose of the invention can be realized by the following technical scheme:
a preparation method of a crystal type composite gel electrolyte comprises the following steps:
(1) adding the gelling component and soluble salt into water, and stirring until the gelling component and the soluble salt are completely dissolved to form a transparent and uniform solution, so as to obtain a gel precursor solution;
(2) gelling the gel precursor solution obtained in the step (1) to prepare hydrogel containing saturated soluble salt;
(3) and (3) placing crystal seeds of corresponding soluble salt above the hydrogel prepared in the step (2) to trigger the directional precipitation of the supersaturated soluble salt in the hydrogel, thereby obtaining the crystalline composite gel electrolyte.
Preferably, in step (1): the gel-forming component is a monomer polymerization system or a physical gel-forming system.
Preferably, the monomer polymerization system comprises a monomer, a cross-linking agent and an ultraviolet light initiator, wherein the monomer is an acrylamide monomer or an acrylate monomer, the cross-linking agent is N, N' -Methylene Bisacrylamide (MBAA), and the ultraviolet light initiator is 2, 2-Diethoxyacetophenone (DEAP).
Preferably, the physical gel-forming system only contains a high molecular substance which is one or more of gelatin and hydroxymethyl cellulose, and the addition amount of the high molecular substance is 5-15% of the mass of water.
Preferably, the monomer is one or more of acrylamide (AAm), N-methylolacrylamide (N-MMAA), and 3- (2-methacryloyloxyethyldimethylamino) propanesulfonate (DMAPS).
Preferably, the addition amount of the monomer is 10-20% of the total weight of water, the addition amount of the cross-linking agent is 0.1-1% of the total weight of the monomer, and the addition amount of the ultraviolet initiator is 0.1-1% of the total weight of the monomer.
Preferably, when the rubber-forming component is a monomer polymerization system, step (c)2) The glue forming mode in the process is as follows: placing the gel precursor solution in a light intensity of 25-30 mW/cm2The reaction time is 10-30 min;
when the gel forming component is a physical gel forming system, the gel forming mode in the step (2) is as follows: standing at room temperature for cooling for 30 min.
Preferably, in step (1): the soluble salt is anhydrous sodium acetate (NaAc) or anhydrous sodium thiosulfate (Na)2S2O3) Anhydrous magnesium sulfate (MgSO)4) In one, the amount of soluble salt added is from 0.4 times the mass of water to the maximum solubility of the soluble salt.
Preferably, in step (1): stirring at 80 deg.C for 5-30 min.
An application of a crystal type composite gel electrolyte in an energy storage device.
The process conditions in the present invention are the most suitable preparation conditions. The heating is for the rapid dissolution of soluble salt, the solution is easy to boil due to overhigh temperature, and the salt is slowly dissolved even is not dissolved due to overlow temperature; the illumination intensity corresponds to the reaction time, and the required reaction time is prolonged if the illumination intensity is too low; the addition amount of reactants can affect the performance of the finally obtained composite gel electrolyte, especially the mechanical performance of the finally obtained composite gel electrolyte, for example, the mechanical strength of the composite gel electrolyte can be reduced due to the low content of the monomer or the cross-linking agent, and even no gel is formed; the addition amount of the soluble salt affects the mechanical strength of the composite gel electrolyte and also affects the ionic conductivity of the composite gel electrolyte, and the higher the addition amount is, the higher the mechanical strength is, but the lower the ionic conductivity is.
The invention obtains the composite gel electrolyte with ultrahigh mechanical strength by inducing the supersaturated salt to directionally crystallize in the common hydrogel matrix containing the supersaturated soluble salt. Wherein the composite gel electrolyte contains a cross-linked polymer hydrogel matrix material, a saturated soluble salt solution and regular soluble salt crystals; the polymer hydrogel matrix can form a three-dimensional space network structure through monomer polymerization or polymer physical crosslinking, and the saturated soluble salt electrolyte aqueous solution and regular soluble salt crystals are filled in gaps of the network structure.
The invention relates to a novel method for preparing a high-strength solid gel electrolyte, which comprises the steps of dissolving excessive soluble salt into a precursor solution at a high temperature, cooling the precursor solution after gelling to form a supersaturated state, and finally initiating crystallization of the soluble salt to obtain the ultrahigh-strength solid gel electrolyte.
The method has the advantages of simple process, strong controllability and easy operation. The solid composite gel electrolyte prepared by the method has ultrahigh mechanical strength, and the maximum compression modulus can reach dozens to hundreds of megapascals, which is thousands to tens of thousands times of that of pure water gel. In addition, because the composite gel still dissolves saturated salt ions after crystallization, the composite gel has good ionic conductivity, and can be used as a safe and reliable solid composite gel electrolyte material to be applied to an energy storage device without introducing other electrolyte salts. In the process of crystallization of soluble salt, a large amount of free water in a hydrogel system can be converted into crystal water, and the electrochemical activity of the water is reduced, so that the electrochemical window of the gel material is improved, and the working voltage and the energy density of an energy storage device are increased.
In addition, due to the existence of the soluble salt crystals, the composite gel can automatically adjust the temperature of the material through dissolution heat absorption or crystallization heat release, becomes a potential constant temperature material, and can maintain the temperature stability of the system in the phase change process, so that the energy storage device applying the electrolyte has longer service life under the condition of sudden fire and has certain disaster prevention capability.
Compared with the prior art, the invention has the following beneficial effects:
(1) compared with the traditional hydrogel electrolyte, the crystalline composite gel electrolyte prepared by the invention has higher mechanical strength due to the enhancement effect of the soluble salt crystal and is safer in application of a solid energy storage device;
(2) compared with solid polymer electrolytes and solid ceramic electrolytes, the crystalline composite gel electrolyte prepared by the invention contains more free conductive ions, has higher ionic conductivity, and can enable an energy storage device to obtain better electrochemical performance;
(3) by utilizing the characteristic that soluble salt crystals are dissolved in water, when the energy storage device is assembled, trace water can be smeared on two sides of the electrolyte, so that the composite gel electrolyte on the outer layer is converted into hydrogel electrolyte, a good bonding effect is generated between the hydrogel electrolyte and an electrode material, the device is convenient to assemble, the contact resistance between the electrolyte and the electrode material is reduced, and the electrochemical performance of the device is improved;
(4) in the process of crystallization of soluble salt, a large amount of free water in a hydrogel system is converted into crystal water, so that the electrochemical activity of the water is reduced, the electrochemical window of the gel material is improved, and the working voltage of an energy storage device is improved;
(5) the high-concentration salt in the crystalline composite gel electrolyte can effectively reduce the freezing point of an aqueous solution, broaden the temperature window of the energy storage device and ensure that the energy storage device can still normally work at low temperature;
(6) the soluble salt crystal can be dissolved and absorb heat at high temperature, and crystallized and release heat at low temperature, through the phase change performance, the temperature of the material can be automatically adjusted according to the environmental temperature by the crystallized composite gel electrolyte, and the temperature of the system can be kept stable in a short time even under extreme temperature environments such as burning or liquid nitrogen, so that an energy storage device applying the electrolyte has longer service life under the condition of sudden fire and has certain disaster prevention capability.
(7) The preparation process is simple, and the raw materials are cheap and easy to obtain.
Drawings
FIG. 1 is a scanning electron microscope photograph of a crystalline composite gel electrolyte of example 1;
FIG. 2 is a compression curve diagram of a crystalline composite gel electrolyte of example 1;
FIG. 3 is an AC impedance spectrum of a crystalline composite gel electrolyte of example 1;
FIG. 4 is a linear voltammogram of the crystalline composite gel electrolyte of example 1 used as a supercapacitor;
FIG. 5 is a constant current charge and discharge graph of the crystalline composite gel electrolyte of example 1 used as a supercapacitor at different current densities;
FIG. 6 is a constant current charge and discharge curve diagram of the crystalline composite gel electrolyte of example 2 used as a super capacitor at different temperatures;
FIG. 7 is a schematic view showing the normal operation of the crystalline composite gel electrolyte of example 2 as an ultracapacitor operating in liquid nitrogen;
FIG. 8 is a schematic view showing the normal operation of the crystalline composite gel electrolyte of example 2 in a flame as a supercapacitor.
Detailed Description
The invention is described in detail below with reference to the figures and specific embodiments.
Example 1
0.15g of acrylamide (AAm), 0.45mg of N, N' -Methylenebisacrylamide (MBAA), 1. mu.L of 2, 2-Diethoxyacetophenone (DEAP) and 1.02g of anhydrous sodium acetate (NaAc) were added to 0.85mL of distilled water, and heated and stirred at 80 ℃ for 5 minutes to form a transparent and uniform precursor solution containing a high concentration of sodium acetate. Irradiating the precursor solution with ultraviolet light at 25 deg.C with illumination intensity of about 25mW/cm2And reacting for 15min to obtain the supersaturated sodium acetate-containing hydrogel electrolyte. And placing a grain of sodium acetate crystal above the hydrogel electrolyte to initiate the directional crystallization of supersaturated sodium acetate in the hydrogel to obtain the crystalline high-strength composite gel electrolyte. The compressive modulus of the obtained composite gel electrolyte is 16.27MPa, the ionic conductivity is 4.4mS/cm, and the specific surface area is 2100m2The active carbon per gram is used as an active substance to be assembled into an electric double layer super capacitor, the working voltage is 2V, and the specific capacity obtained under the current density of 1A/g is 120.8F/g.
As shown in FIG. 1, the sample of the crystalline high-strength composite gel electrolyte of the present embodiment has regularly arranged sodium acetate crystals in the SEM image after freeze-drying treatment, and the crystal size is 2-3 μm. As shown in fig. 2, which is a compression curve of the composite gel electrolyte, it can be found by calculation that the compression modulus of the sample of the present embodiment is 16.27MPa, which is much higher than the mechanical strength of the common hydrogel electrolyte. FIG. 3 is an AC impedance spectrum of a crystalline high-strength composite gel electrolyte sample, wherein the sample is a cylinder with a diameter of 1.4cm and a height of 0.9cm, and the ionic conductivity of the composite gel electrolyte measured by an AC impedance method is 4.4mS/cm, and the composite gel electrolyte shows good conductive characteristics.
The obtained crystalline high-strength composite gel electrolyte and the specific surface area of the electrolyte are 2100m2The active carbon electrode per gram is assembled into a double electric layer super capacitor, and a linear volt-ampere scanning test is carried out, so that the result is shown in fig. 4, the decomposition voltage of the composite gel electrolyte is more than 2V and much higher than that of the common hydrogel electrolyte, and higher working voltage and energy density can be provided for energy storage devices such as super capacitors. FIG. 5 is a constant current charge/discharge curve of the supercapacitor at different current densities (0.2A/g-20A/g), and it can be seen from the curve that the supercapacitor using the crystalline high-strength composite gel electrolyte has excellent rate capability.
Example 2
0.15g of 3- (2-methacryloyloxyethyl dimethylamino) propanesulfonate (DMAPS), 0.45mg of N, N' -Methylenebisacrylamide (MBAA), 1. mu.L of 2, 2-Diethoxyacetophenone (DEAP), 1.02g of anhydrous sodium acetate (NaAc) were added to 0.85mL of distilled water, and heated and stirred at 80 ℃ for 5 minutes to form a transparent and uniform precursor solution containing a high concentration of sodium acetate. Irradiating the precursor solution with ultraviolet light at 25 deg.C with illumination intensity of about 25mW/cm2And reacting for 30min to obtain the supersaturated sodium acetate-containing hydrogel electrolyte. And placing a grain of sodium acetate crystal above the hydrogel electrolyte to initiate the directional crystallization of supersaturated sodium acetate in the hydrogel to obtain the crystalline high-strength composite gel electrolyte. The compressive modulus of the obtained composite gel electrolyte is 4.64MPa, the ionic conductivity is 8.9mS/cm, and the specific surface area is 2100m2The active carbon per gram is used as an active substance to be assembled into an electric double layer super capacitor, the working voltage is 2V, and the specific capacity obtained under the current density of 1A/g is 175.9F/g.
The super capacitor of the embodiment is placed at different temperatures (-40 ℃ to 80 ℃) for constant temperature treatment for 30min, and constant current charge and discharge tests are carried out on the super capacitor at a current density of 1A/g, as shown in FIG. 6, the super capacitor can still normally work at different temperatures, and shows good low-temperature performance. As shown in fig. 7 and 8, the supercapacitor of the present embodiment can still normally operate in a short time by being placed in liquid nitrogen (-196 ℃) or flame (>200 ℃), can last for more than 10 seconds compared with a device made of a common hydrogel electrolyte, exhibits a certain ability to resist extreme temperatures, and has a certain disaster-resistant effect when dealing with sudden disasters such as fire.
Example 3
0.15g of acrylamide (AAm), 0.45mg of N, N' -Methylenebisacrylamide (MBAA), 1. mu.L of 2, 2-Diethoxyacetophenone (DEAP), and 0.34g of anhydrous sodium acetate (NaAc) were added to 0.85mL of distilled water, and heated and stirred at 80 ℃ for 5 minutes to form a transparent and uniform precursor solution containing a high concentration of sodium acetate. Irradiating the precursor solution with ultraviolet light at 25 deg.C with illumination intensity of about 25mW/cm2And reacting for 15min to obtain the supersaturated sodium acetate-containing hydrogel electrolyte. And placing a grain of sodium acetate crystal above the hydrogel electrolyte to initiate the directional crystallization of supersaturated sodium acetate in the hydrogel to obtain the crystalline high-strength composite gel electrolyte. The compressive modulus of the obtained composite gel electrolyte is 0.018MPa, and the ionic conductivity is 50.8 mS/cm.
Example 4
0.15g of acrylamide (AAm), 0.45mg of N, N' -Methylenebisacrylamide (MBAA), 1. mu.L of 2, 2-Diethoxyacetophenone (DEAP) and 0.51g of anhydrous sodium acetate (NaAc) were added to 0.85mL of distilled water, and heated and stirred at 80 ℃ for 5 minutes to form a transparent and uniform precursor solution containing a high concentration of sodium acetate. Irradiating the precursor solution with ultraviolet light at 25 deg.C with illumination intensity of about 25mW/cm2And reacting for 15min to obtain the supersaturated sodium acetate-containing hydrogel electrolyte. And placing a grain of sodium acetate crystal above the hydrogel electrolyte to initiate the directional crystallization of supersaturated sodium acetate in the hydrogel to obtain the crystalline high-strength composite gel electrolyte. The compressive modulus of the obtained composite gel electrolyte is 0.034MPa, and the ionic conductivity is 38.3 mS/cm.
Example 5
0.15g of acrylamide (AAm), 0.45mg of N, N' -Methylenebisacrylamide (MBAA), 1. mu.L of 2, 2-Diethoxyacetophenone (DEAP), 0.68g of anhydrous sodium acetate (NaAc) were added to 0.85mL of distilled water, heated and stirred at 80 ℃ for 5min,a transparent and uniform precursor solution containing a high concentration of sodium acetate is formed. Irradiating the precursor solution with ultraviolet light at 25 deg.C with illumination intensity of about 25mW/cm2And reacting for 15min to obtain the supersaturated sodium acetate-containing hydrogel electrolyte. And placing a grain of sodium acetate crystal above the hydrogel electrolyte to initiate the directional crystallization of supersaturated sodium acetate in the hydrogel to obtain the crystalline high-strength composite gel electrolyte. The compressive modulus of the obtained composite gel electrolyte is 0.48MPa, and the ionic conductivity is 20.5 mS/cm.
Example 6
0.15g of acrylamide (AAm), 0.45mg of N, N' -Methylenebisacrylamide (MBAA), 1. mu.L of 2, 2-Diethoxyacetophenone (DEAP) and 0.85g of anhydrous sodium acetate (NaAc) were added to 0.85mL of distilled water, and heated and stirred at 80 ℃ for 5 minutes to form a transparent and uniform precursor solution containing a high concentration of sodium acetate. Irradiating the precursor solution with ultraviolet light at 25 deg.C with illumination intensity of about 25mW/cm2And reacting for 15min to obtain the supersaturated sodium acetate-containing hydrogel electrolyte. And placing a grain of sodium acetate crystal above the hydrogel electrolyte to initiate the directional crystallization of supersaturated sodium acetate in the hydrogel to obtain the crystalline high-strength composite gel electrolyte. The compressive modulus of the obtained composite gel electrolyte is 3.62MPa, and the ionic conductivity is 10.8 mS/cm.
Example 7
0.15g of acrylamide (AAm), 0.45mg of N, N' -Methylenebisacrylamide (MBAA), 1. mu.L of 2, 2-Diethoxyacetophenone (DEAP) and 1.19g of anhydrous sodium acetate (NaAc) were added to 0.85mL of distilled water, and heated and stirred at 80 ℃ for 5 minutes to form a transparent and uniform precursor solution containing a high concentration of sodium acetate. Irradiating the precursor solution with ultraviolet light at 25 deg.C with illumination intensity of about 25mW/cm2And reacting for 15min to obtain the supersaturated sodium acetate-containing hydrogel electrolyte. And placing a grain of sodium acetate crystal above the hydrogel electrolyte to initiate the directional crystallization of supersaturated sodium acetate in the hydrogel to obtain the crystalline high-strength composite gel electrolyte. The compressive modulus of the obtained composite gel electrolyte is 37.65MPa, and the ionic conductivity is 2.6 mS/cm.
Example 8
0.15g of acrylamide (AAm), 0.45mg of N, N' -Methylenebisacrylamide (MBAA), 1. mu.L of 2, 2-Diethoxyacetophenone (DEAP) and 1.36g of anhydrous sodium acetate (NaAc) were added to 0.85mL of distilled water, and heated and stirred at 80 ℃ for 5 minutes to form a transparent and uniform precursor solution containing a high concentration of sodium acetate. Irradiating the precursor solution with ultraviolet light at 25 deg.C with illumination intensity of about 25mW/cm2And reacting for 15min to obtain the supersaturated sodium acetate-containing hydrogel electrolyte. And placing a grain of sodium acetate crystal above the hydrogel electrolyte to initiate the directional crystallization of supersaturated sodium acetate in the hydrogel to obtain the crystalline high-strength composite gel electrolyte. The compressive modulus of the obtained composite gel electrolyte is 474.24MPa, and the ionic conductivity is 0.9 mS/cm.
Example 9
0.075g of acrylamide (AAm) and 0.075g of 3- (2-methacryloyloxyethyldimethylamino) propanesulfonate (DMAPS), 0.45mg of N, N' -Methylenebisacrylamide (MBAA), 1. mu.L of 2, 2-Diethoxyacetophenone (DEAP), 1.02g of anhydrous sodium acetate (NaAc) were added to 0.85mL of distilled water, and heated and stirred at 80 ℃ for 5min to form a clear and uniform precursor solution containing a high concentration of sodium acetate. Irradiating the precursor solution with ultraviolet light at 25 deg.C with illumination intensity of about 25mW/cm2And reacting for 30min to obtain the supersaturated sodium acetate-containing hydrogel electrolyte. And placing a grain of sodium acetate crystal above the hydrogel electrolyte to initiate the directional crystallization of supersaturated sodium acetate in the hydrogel to obtain the crystalline high-strength composite gel electrolyte. The compressive modulus of the obtained composite gel electrolyte is 10.21MPa, and the ionic conductivity is 5.6 mS/cm.
Example 10
0.15g N-methylolacrylamide (N-MMAA), 0.45mg of N, N' -Methylenebisacrylamide (MBAA), 1. mu.L of 2, 2-Diethoxyacetophenone (DEAP), 1.02g of anhydrous sodium acetate (NaAc) were added to 0.85mL of distilled water, and heated and stirred at 80 ℃ for 5min to form a transparent and uniform precursor solution containing a high concentration of sodium acetate. Irradiating the precursor solution with ultraviolet light at 25 deg.C with illumination intensity of about 25mW/cm2And reacting for 30min to obtain the supersaturated sodium acetate-containing hydrogel electrolyte. Placing a grain of sodium acetate crystal above the hydrogel electrolyteAnd (3) inducing the supersaturated sodium acetate in the hydrogel to directionally crystallize to obtain the crystalline high-strength composite gel electrolyte. The compressive modulus of the obtained composite gel electrolyte is 5.55MPa, and the ionic conductivity is 7.6 mS/cm.
Example 11
0.1g of gelatin (AG) and 1.08g of anhydrous sodium acetate (NaAc) were added to 0.9mL of distilled water, and the mixture was heated and stirred at 80 ℃ for 30 minutes to form a transparent and uniform precursor solution containing a high concentration of sodium acetate. And cooling the precursor liquid for 30min at the temperature of 25 ℃ to prepare the supersaturated sodium acetate-containing hydrogel electrolyte. And placing a grain of sodium acetate crystal above the hydrogel electrolyte to initiate the directional crystallization of supersaturated sodium acetate in the hydrogel to obtain the crystalline high-strength composite gel electrolyte. The compressive modulus of the obtained composite gel electrolyte is 42.70MPa, and the ionic conductivity is 6.1 mS/cm.
Example 12
0.1g of hydroxymethyl cellulose (CMC) and 1.08g of anhydrous sodium acetate (NaAc) were added to 0.9mL of distilled water, and the mixture was heated and stirred at 80 ℃ for 30 minutes to form a transparent and uniform precursor solution containing a high concentration of sodium acetate. And cooling the precursor liquid for 30min at the temperature of 25 ℃ to prepare the supersaturated sodium acetate-containing hydrogel electrolyte. And placing a grain of sodium acetate crystal above the hydrogel electrolyte to initiate the directional crystallization of supersaturated sodium acetate in the hydrogel to obtain the crystalline high-strength composite gel electrolyte. The compressive modulus of the obtained composite gel electrolyte is 23.87MPa, and the ionic conductivity is 7.9 mS/cm.
Example 13
0.1g of hydroxymethyl cellulose (CMC), 1.8g of anhydrous sodium thiosulfate (Na)2S2O3) Added to 0.9mL of distilled water, and heated and stirred at 80 ℃ for 30min to form a transparent and uniform precursor solution containing a high concentration of sodium thiosulfate. And cooling the precursor liquid for 30min at the temperature of 25 ℃ to prepare the supersaturated sodium thiosulfate-containing hydrogel electrolyte. And placing a particle of sodium thiosulfate crystal above the hydrogel electrolyte to initiate the directional crystallization of supersaturated sodium thiosulfate in the hydrogel to obtain the crystalline high-strength composite gel electrolyte. The resulting composite gel electrolyte had a compressive modulus of 6965MPa, and an ionic conductivity of 4.2 mS/cm.
Example 14
0.15g of acrylamide (AAm), 0.45mg of N, N' -Methylenebisacrylamide (MBAA), 1. mu.L of 2, 2-Diethoxyacetophenone (DEAP), 0.425g of anhydrous magnesium sulfate (MgSO)4) The resulting mixture was added to 0.85mL of distilled water, and heated and stirred at 80 ℃ for 5 minutes to form a transparent and uniform precursor solution containing magnesium sulfate at a high concentration. Irradiating the precursor solution with ultraviolet light at 25 deg.C with illumination intensity of about 25mW/cm2And reacting for 15min to obtain the supersaturated magnesium sulfate-containing hydrogel electrolyte. And placing a magnesium sulfate crystal above the hydrogel electrolyte to initiate the directional crystallization of supersaturated magnesium sulfate in the hydrogel to obtain the crystalline high-strength composite gel electrolyte. The compressive modulus of the obtained composite gel electrolyte is 0.13MPa, and the ionic conductivity is 14.4 mS/cm.
Example 15
0.085g of acrylamide (AAm), 0.85mg of N, N' -Methylenebisacrylamide (MBAA), 0.85mg of 2, 2-Diethoxyacetophenone (DEAP) and 1.36g of anhydrous sodium acetate (NaAc) were added to 0.85mL of distilled water, and heated and stirred at 80 ℃ for 20min to form a transparent and uniform precursor solution containing a high concentration of sodium acetate. Irradiating the precursor solution with ultraviolet light at 25 deg.C with illumination intensity of about 30mW/cm2And reacting for 10min to obtain the supersaturated sodium acetate-containing hydrogel electrolyte. And placing a grain of sodium acetate crystal above the hydrogel electrolyte to initiate the directional crystallization of supersaturated sodium acetate in the hydrogel to obtain the crystalline high-strength composite gel electrolyte.
Example 16
0.17g of acrylamide (AAm), 0.085mg of N, N' -Methylenebisacrylamide (MBAA), 0.085mg of 2, 2-Diethoxyacetophenone (DEAP), and 0.51g of anhydrous sodium acetate (NaAc) were added to 0.85mL of distilled water, and heated and stirred at 80 ℃ for 5min to form a transparent and uniform precursor solution containing a high concentration of sodium acetate. Irradiating the precursor solution with ultraviolet light at 25 deg.C with illumination intensity of about 27mW/cm2And reacting for 10min to obtain the supersaturated sodium acetate-containing hydrogel electrolyte. Placing a grain of sodium acetate crystal above the hydrogel electrolyte to initiate the hydrogel interiorThe supersaturated sodium acetate is directionally crystallized to obtain the crystalline high-strength composite gel electrolyte.
Example 17
0.1275g of acrylamide (AAm), 0.1275mg of N, N' -Methylenebisacrylamide (MBAA), 0.1275mg of 2, 2-Diethoxyacetophenone (DEAP) and 0.51g of anhydrous sodium acetate (NaAc) were added to 0.85mL of distilled water, and the mixture was heated and stirred at 80 ℃ for 20 minutes to form a transparent and uniform precursor solution containing a high concentration of sodium acetate. Irradiating the precursor solution with ultraviolet light at 25 deg.C with illumination intensity of about 27mW/cm2And reacting for 10min to obtain the supersaturated sodium acetate-containing hydrogel electrolyte. And placing a grain of sodium acetate crystal above the hydrogel electrolyte to initiate the directional crystallization of supersaturated sodium acetate in the hydrogel to obtain the crystalline high-strength composite gel electrolyte.
Example 18
0.0425g of gelatin (AG) and 1.08g of anhydrous sodium acetate (NaAc) were added to 0.85mL of distilled water, and the mixture was heated and stirred at 80 ℃ for 30 minutes to form a transparent and uniform precursor solution containing a high concentration of sodium acetate. And cooling the precursor liquid for 30min at the temperature of 25 ℃ to prepare the supersaturated sodium acetate-containing hydrogel electrolyte. And placing a grain of sodium acetate crystal above the hydrogel electrolyte to initiate the directional crystallization of supersaturated sodium acetate in the hydrogel to obtain the crystalline high-strength composite gel electrolyte.
Example 19
0.135g of hydroxymethyl cellulose (CMC) and 1.08g of anhydrous sodium acetate (NaAc) were added to 0.9mL of distilled water, and the mixture was heated and stirred at 80 ℃ for 30 minutes to form a transparent and uniform precursor solution containing a high concentration of sodium acetate. And cooling the precursor liquid for 30min at the temperature of 25 ℃ to prepare the supersaturated sodium acetate-containing hydrogel electrolyte. And placing a grain of sodium acetate crystal above the hydrogel electrolyte to initiate the directional crystallization of supersaturated sodium acetate in the hydrogel to obtain the crystalline high-strength composite gel electrolyte.
The embodiments described above are described to facilitate an understanding and use of the invention by those skilled in the art. It will be readily apparent to those skilled in the art that various modifications to these embodiments may be made, and the generic principles described herein may be applied to other embodiments without the use of the inventive faculty. Therefore, the present invention is not limited to the above embodiments, and those skilled in the art should make improvements and modifications within the scope of the present invention based on the disclosure of the present invention.

Claims (9)

1. A preparation method of a crystal type composite gel electrolyte is characterized by comprising the following steps:
(1) adding the gelling component and soluble salt into water, and stirring until the gelling component and the soluble salt are completely dissolved to form a transparent and uniform solution, so as to obtain a gel precursor solution;
(2) gelling the gel precursor solution obtained in the step (1) to prepare hydrogel containing saturated soluble salt;
(3) and (3) placing crystal seeds corresponding to the soluble salt above the hydrogel prepared in the step (2) to obtain the crystalline composite gel electrolyte.
2. The method for preparing a crystalline composite gel electrolyte according to claim 1, wherein in the step (1): the gel-forming component is a monomer polymerization system or a physical gel-forming system.
3. The method for preparing the crystalline composite gel electrolyte according to claim 2, wherein the monomer polymerization system comprises a monomer, a cross-linking agent and an ultraviolet light initiator, the monomer is an acrylamide monomer or an acrylate monomer, the cross-linking agent is N, N' -methylenebisacrylamide, and the ultraviolet light initiator is 2, 2-diethoxyacetophenone;
the physical gelling system only contains a high molecular substance which is one or more of gelatin or hydroxymethyl cellulose, and the addition amount of the high molecular substance is 5-15% of the mass of water.
4. The method of claim 3, wherein the monomer is one or more of acrylamide, N-methylolacrylamide, and 3- (2-methacryloyloxyethyldimethylamino) propane sulfonate.
5. The preparation method of the crystalline composite gel electrolyte as claimed in claim 3, wherein the addition amount of the monomer is 10-20% of the total weight of water, the addition amount of the cross-linking agent is 0.1-1% of the total weight of the monomer, and the addition amount of the ultraviolet initiator is 0.1-1% of the total weight of the monomer.
6. The method of claim 2, wherein when the gel-forming component is a monomer polymerization system, the gel-forming manner in step (2) is as follows: placing the gel precursor solution in a light intensity of 25-30 mW/cm2The reaction time is 10-30 min;
when the gel forming component is a physical gel forming system, the gel forming mode in the step (2) is as follows: standing at room temperature for cooling for 30 min.
7. The method for preparing a crystalline composite gel electrolyte according to claim 1, wherein in the step (1): the soluble salt is one of anhydrous sodium acetate, anhydrous sodium thiosulfate and anhydrous magnesium sulfate, and the addition amount of the soluble salt is 0.4 times of the mass of water to reach the maximum solubility of the soluble salt.
8. The method for preparing a crystalline composite gel electrolyte according to claim 1, wherein in the step (1): stirring at 80 deg.C for 5-30 min.
9. A crystalline composite gel electrolyte prepared by the method of any one of claims 1-8.
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