CN113488706A - Method for preparing hydrogel electrolyte, hydrogel electrolyte and energy storage device - Google Patents

Method for preparing hydrogel electrolyte, hydrogel electrolyte and energy storage device Download PDF

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CN113488706A
CN113488706A CN202110673340.0A CN202110673340A CN113488706A CN 113488706 A CN113488706 A CN 113488706A CN 202110673340 A CN202110673340 A CN 202110673340A CN 113488706 A CN113488706 A CN 113488706A
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polyvinyl alcohol
hydrogel
hydrogel electrolyte
electrolyte
sulfate
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CN113488706B (en
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黄江
王铮莹
盛轲焱
左晨
陈太炎
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Huazhong University of Science and Technology
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/36—Accumulators not provided for in groups H01M10/05-H01M10/34
    • H01M10/38—Construction or manufacture
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/36—Accumulators not provided for in groups H01M10/05-H01M10/34
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2300/00—Electrolytes
    • H01M2300/0085—Immobilising or gelification of electrolyte
    • 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
    • Y02E60/10—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
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

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Abstract

The invention discloses a preparation method of a hydrogel electrolyte and the hydrogel electrolyte obtained by the preparation method, which comprises the following steps: providing an aqueous solution of polyvinyl alcohol; adding glycerol into the aqueous solution of the metal sulfate, and uniformly mixing; uniformly mixing a mixed solution of metal sulfate and glycerol with an aqueous solution of polyvinyl alcohol; and irradiating the mixed solution containing the metal sulfate, the glycerin and the polyvinyl alcohol. The preparation method of the hydrogel electrolyte provided by the invention has a short preparation period, and no additional component is required to be added, so that the obtained hydrogel electrolyte has high ionic conductivity.

Description

Method for preparing hydrogel electrolyte, hydrogel electrolyte and energy storage device
Technical Field
The invention relates to the field of electrolyte materials, in particular to a preparation method of a hydrogel electrolyte and the hydrogel electrolyte obtained by the preparation method.
Background
With the development of electronic devices, flexible electronic devices are also receiving more and more attention. For flexible electronic devices, flexible energy storage devices are one of the key technical points, which requires that the flexible energy storage devices not only have a considerable capacity, but also have a certain degree of flexibility, and can be stretched or bent.
The use of liquid electrolytes in the above-described flexible energy storage devices has the following problems: in the process of bending deformation of the energy storage device, the liquid electrolyte is easy to generate leakage risk; and the liquid electrolyte can generate dislocation under strain, so that the conductivity of the liquid electrolyte is unstable. The above problems can be solved by applying the hydrogel electrolyte to a flexible energy storage device. Firstly, the hydrogel electrolyte can avoid the leakage problem of the liquid electrolyte; secondly, the hydrogel electrolyte can maintain physical integrity and flexibility under various mechanical deformations; finally, the gel electrolyte with limited free water and good adsorption affinity can slow down the dissolution of active substances and inhibit the growth of dendritic crystals of metal electrodes, thereby improving the electrochemical stability.
In the prior art, a hydrogel electrolyte is generally prepared by a freeze-thaw cycle method and an ultraviolet curing method and is applied to a flexible energy storage device. However, the freeze-thaw cycling method for preparing the hydrogel is long in period and complex in operation; and the ultraviolet curing method needs to add a photoinitiator in the process of preparing the hydrogel, so that the method does not meet the requirement of green environmental protection.
Disclosure of Invention
In view of the above, the main object of the present invention is to provide a method for preparing a hydrogel electrolyte with a short preparation period without adding additional components, and a hydrogel electrolyte obtained thereby.
The first aspect of the present invention provides a method for preparing a hydrogel electrolyte, comprising the steps of:
providing an aqueous solution of polyvinyl alcohol;
adding glycerol into the aqueous solution of the metal sulfate, and uniformly mixing;
uniformly mixing a mixed solution of metal sulfate and glycerol with an aqueous solution of polyvinyl alcohol; and
the mixed solution containing the metal sulfate, glycerin and polyvinyl alcohol is irradiated.
According to one embodiment of the present invention, the components of the method are used in the following amounts, based on the total weight of the hydrogel electrolyte:
2-10 wt% of polyvinyl alcohol;
1-5 wt% of glycerol;
2-8 wt% of metal sulfate; and
80-92 wt% of water.
According to one embodiment of the present invention, the degree of polymerization of the polyvinyl alcohol is 1700 to 2400, and the degree of alcoholysis is 88 to 99%. Preferably, the polymerization degree of the polyvinyl alcohol is 1700-2000; the alcoholysis degree of the polyvinyl alcohol is 97-99%. More preferably, the degree of polymerization of the polyvinyl alcohol is about 1800; the alcoholysis degree of the polyvinyl alcohol is 98-99%.
In the hydrogel electrolyte, polyvinyl alcohol is used as a matrix of the hydrogel, and the hydrogel electrolyte can obtain better mechanical properties within the polymerization degree range.
According to one embodiment of the present invention, the dissolution temperature and dissolution time of the polyvinyl alcohol in water are not particularly limited as long as complete dissolution of the polyvinyl alcohol can be ensured. Considering that the polymer is generally dissolved slowly at room temperature, the temperature may be increased appropriately to accelerate the dissolution of the polymer. Of course, in order to accelerate the dissolution of the polymer, it is also possible to perform appropriate stirring during the dissolution of the polymer. For example, the polyvinyl alcohol can be dissolved for 2 to 3 hours under stirring at 90 to 100 ℃.
According to one embodiment of the present invention, the preferable content of the polyvinyl alcohol is 4 to 8 wt%; more preferably, the polyvinyl alcohol is present in an amount of about 6 wt%.
In the hydrogel electrolyte of the present invention, glycerin serves as a physical crosslinking agent, providing a plurality of physical crosslinking points. So that hydrogen bond crosslinking can be formed among the polyvinyl alcohol, the glycerol and the water, and the crosslinking strength is increased.
According to one embodiment of the invention, the preferred content of glycerol is 2 to 4 wt%; more preferably, the glycerol is present in an amount of about 3 wt%.
In the hydrogel electrolyte of the present invention, the metal ions in the metal sulfate are transported in the polymer matrix of the polyvinyl alcohol as conductive ions.
According to an embodiment of the present invention, the metal sulfate may be selected from one or two of zinc sulfate, sodium sulfate, and manganese sulfate. Wherein the metal sulfate is preferably zinc sulfate, and the metal sulfate is preferably a combination of zinc sulfate and manganese sulfate. More preferably, the metal sulfate is zinc sulfate.
According to one embodiment of the present invention, the preferable content of the metal sulfate is 3 to 7 wt%. More preferably, the content of the metal sulfate is 4-5 wt%.
The hydrogel electrolyte adopts different metal ions, and can play a role in ion transmission. Different metal ions can be matched with different flexible energy storage devices. For example: in an aqueous zinc ion battery, zinc is used as a negative electrode material and manganese dioxide is used as a positive electrode material, and if the hydrogel electrolyte of the present invention is to be applied to a zinc ion battery, the hydrogel electrolyte must be capable of transporting zinc ions and manganese ions simultaneously.
According to one embodiment of the invention, the mass ratio of the polyvinyl alcohol to the metal sulfate is 1-1.5: 1. Preferably, the mass ratio of the polyvinyl alcohol to the metal sulfate is 1-1.3: 1. For example, the mass ratio of the polyvinyl alcohol to the metal sulfate is 1.1, 1.2, or 1.3.
According to one embodiment of the present invention, the water in the hydrogel electrolyte may be deionized water, double distilled water, or the like. The preferable content of the water is 82-90 wt%; more preferably, the water content is about 86 wt%.
According to one embodiment of the invention, the irradiation produces electron beam irradiation using an electron accelerator. The irradiation dose is 10-50 kGy. As an example, the irradiation dose may be 10kGy, 20kGy, 30kGy, 40kGy, and 50 kGy. Preferably, the dose of electron beam irradiation is 10-30 kGy. Most preferably, the dose of electron beam irradiation is about 30 kGy.
According to one embodiment of the present invention, the hydrogel electrolyte may be formed into a desired shape by a mold. Specifically, a mixed solution containing a metal sulfate, glycerin, and polyvinyl alcohol may be placed in a mold before irradiation is performed. The mold must be able to withstand irradiation. For example, the mold may be a glass plate, and the precursor solution containing the metal sulfate, glycerol, and polyvinyl alcohol may be directly spread on the glass plate, i.e., may be irradiated, so that the precursor solution is crosslinked. The second aspect of the present invention provides a hydrogel electrolyte obtained by the above method for preparing a hydrogel electrolyte.
A third aspect of the invention provides an energy storage device comprising the hydrogel electrolyte.
The energy storage device is an aqueous ionic energy storage device, in particular a battery, such as in particular: an aqueous zinc ion battery and a mixed aqueous sodium zinc ion battery.
For example: the hydrogel electrolyte can transmit zinc ions and manganese ions, and can be used in a water-based zinc ion battery. Another example is: the hydrogel electrolyte can also transmit sodium ions and can be used in a water-based sodium ion battery.
In the preparation method of the hydrogel electrolyte, polyvinyl alcohol is used as a matrix, glycerol is used as a physical cross-linking agent, and metal sulfate is used as conductive ions and is prepared by irradiation. The method of the present invention has a short preparation period and does not require the addition of additional components, and the hydrogel electrolyte obtained by the method of the present invention also has improved ionic conductivity.
Drawings
FIG. 1 is an infrared analysis spectrum of polyvinyl alcohol, glycerin, and hydrogels obtained in examples 1 to 5 and comparative example 1;
FIGS. 2A to 2C are thermal stability analyses of hydrogels obtained from examples and comparative examples;
FIGS. 3A to 3C are graphs of ionic conductivities of hydrogels obtained from examples and comparative examples;
fig. 4 is a diagram of electrochemical windows of hydrogels according to examples and comparative examples.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention and the accompanying drawings, and it is apparent that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be obtained by a person skilled in the art without any inventive step based on the embodiments of the present invention, are within the scope of the present invention.
Examples 1 to 5
4g of polyvinyl alcohol are added to 50ml of deionized water and stirred at 90 ℃ for 2h until a homogeneous, transparent solution is formed. 2g of glycerol were added to 10ml of an aqueous solution containing 2M zinc sulphate and mixed well. Adding a mixed solution of zinc sulfate and glycerol into a polyvinyl alcohol aqueous solution, and uniformly mixing to obtain a precursor solution.
The precursor solution was spread flat on a purpose-made dish and subsequently used with an electron accelerator at 200keV, Air gap40mm, N2And carrying out irradiation crosslinking under the atmosphere. The doses irradiated in examples 1 to 5 were 10kGy, 20kGy, 30kGy, 40kGy and 50kGy, respectively.
Examples 6 to 10
4g of polyvinyl alcohol are added to 50ml of deionized water and stirred at 90 ℃ for 2h until a homogeneous, transparent solution is formed. 2g of glycerol was added to 10ml of an aqueous solution containing 2M zinc sulphate and 0.2M manganese sulphate and mixed well. Adding a mixed solution of zinc sulfate, manganese sulfate and glycerol into a polyvinyl alcohol aqueous solution, and uniformly mixing to obtain a precursor solution.
The precursor solution was spread flat on a purpose-made dish and subsequently used with an electron accelerator at 200keV, Air gap40mm, N2And carrying out irradiation crosslinking under the atmosphere. The doses irradiated in examples 6 to 10 were 10kGy, 20kGy, 30kGy, 40kGy and 50kGy, respectively.
Examples 11 to 15
4g of polyvinyl alcohol are added to 50ml of deionized water and stirred at 90 ℃ for 2h until a homogeneous, transparent solution is formed. 2g of glycerol was added to 10ml of an aqueous solution containing 2M zinc sulphate and 0.1M sodium sulphate and mixed well. Adding a mixed solution of zinc sulfate, sodium sulfate and glycerol into a polyvinyl alcohol aqueous solution, and uniformly mixing to obtain a precursor solution.
The precursor solution was spread flat on a purpose-made dish and subsequently used with an electron accelerator at 200keV, Air gap40mm, N2And carrying out irradiation crosslinking under the atmosphere. The doses irradiated in examples 11 to 15 were 10kGy, 20kGy, 30kGy, 40kGy and 50kGy, respectively.
Comparative example 1
4g of polyvinyl alcohol are added to 50ml of deionized water and stirred at 90 ℃ for 2h until a homogeneous, transparent solution is formed. 2g of glycerol were added to 10ml of an aqueous solution containing 2M zinc sulphate and mixed well. Adding a mixed solution of zinc sulfate and glycerol into a polyvinyl alcohol aqueous solution, and uniformly mixing to obtain a precursor solution.
The precursor solution was inverted on a glass plate and gelled for a certain time at room temperature to prepare the hydrogel electrolyte of comparative example 1.
Comparative example 2
4g of polyvinyl alcohol are added to 50ml of deionized water and stirred at 90 ℃ for 2h until a homogeneous, transparent solution is formed. 2g of glycerol was added to 10ml of an aqueous solution containing 2M zinc sulphate and 0.2M manganese sulphate and mixed well. Adding a mixed solution of zinc sulfate, manganese sulfate and glycerol into a polyvinyl alcohol aqueous solution, and uniformly mixing to obtain a precursor solution.
The precursor solution was inverted onto a glass plate and gelled for a certain time at room temperature to prepare the hydrogel electrolyte of comparative example 2.
Comparative example 3
4g of polyvinyl alcohol are added to 50ml of deionized water and stirred at 90 ℃ for 2h until a homogeneous, transparent solution is formed. 2g of glycerol was added to 10ml of an aqueous solution containing 2M zinc sulphate and 0.1M sodium sulphate and mixed well. Adding a mixed solution of zinc sulfate, sodium sulfate and glycerol into a polyvinyl alcohol aqueous solution, and uniformly mixing to obtain a precursor solution.
The precursor solution was inverted onto a glass plate and gelled for a certain time at room temperature to prepare the hydrogel electrolyte of comparative example 3.
Comparative example 4
4g of polyvinyl alcohol are added to 50ml of deionized water and stirred at 90 ℃ for 2h until a homogeneous, transparent solution is formed. 2g of glycerol were added to 10ml of an aqueous solution containing 2M zinc sulphate and 0.1M sodium sulphate, 0.38g of borax was added to the metal salt solution and stirred homogeneously at 60 ℃ for about 30 min. Adding a mixed solution containing zinc sulfate, sodium sulfate, glycerol and borax into a polyvinyl alcohol aqueous solution, and uniformly mixing to obtain a precursor solution.
The precursor solution was inverted onto a glass plate and gelled for a certain time at room temperature to prepare the hydrogel electrolyte of comparative example 4.
Test example 1:
infrared analysis using Nicolet iS50R at N2Under the atmosphere, a KBr tabletting method is adopted to prepare a sample, and the observation wavelength range is 500-4000 cm-1. The results of the tests on polyvinyl alcohol, glycerin, and the hydrogels obtained in examples 1 to 5 and comparative example 1 are shown in FIG. 1.
FIG. 1 is a graph of infrared analysis of hydrogels obtained from polyvinyl alcohol, glycerin, examples 1 to 5, and comparative example 1, with wavenumber (wavenumber) on the abscissa and cm on the abscissa-1The ordinate represents the transmittance (transmittance) and the ordinate represents%. The hydrogels of examples 1 to 5 and comparative example 1 all included polyvinyl alcohol (PVA), glycerol, zinc sulfate, and water, and thus the hydrogels of examples 1 to 5 and comparative example 1 all had characteristic peaks of PVA and glycerol at the same time. And, as the irradiation dose increased to 30kGy, the hydroxyl group peak of water shifted to the right, i.e., from the irradiation doses of 10kGy, 20kGy and 30kGy, respectively, corresponding to examples 1, 2 and 3, respectively, the hydroxyl group peak of water was located at 3198cm, respectively-1、3201cm-1And 3249cm-1. This indicates that glycerol, as a physical cross-linking agent, forms hydrogen bond cross-links with PVA in the hydrogel electrolyte under irradiation conditions. Whereas when the irradiation dose was increased to 40kGy and 50kGy, the hydroxyl peak of water disappeared in correspondence with examples 4 and 5, respectively. This suggests that as the irradiation dose increases, hydrogen bonds in the hydrogel may be broken and some degradation of the hydrogel may occur.
Test example 2:
thermal stability analysis using Netzsh STA449F3 at N2Under the atmosphere, the temperature is raised from room temperature to 600 ℃, and the temperature raising rate is 10 ℃/min. N is a radical of2The test is carried out under the atmosphere. The abscissa of FIGS. 2A-2C is temperature (temperature), the abscissa is in degrees C, the ordinate is weight percent (weight), and the ordinate is in%. The hydrogels obtained in examples 1 to 5 and comparative example 1 were tested, and the results are shown in FIG. 2A. The hydrogels obtained in examples 6, 8 and 10 and comparative example 2 were tested, respectively, and the results are shown in fig. 2B. The hydrogels obtained from examples 13 and 15, and comparative examples 3 and 4, respectively, were tested and the results are shown in figure 2C.
FIGS. 2A-2C are hydrogel thermal stability analyses of various examples and comparative examples. The left panel of fig. 2A is an enlarged view of the thermogravimetric analysis in the low temperature region. As can be seen from the analysis of the left image in FIG. 2A, the thermal stability of the non-irradiated hydrogel (corresponding to comparative example 1) was between that of the irradiated hydrogels (corresponding to examples 1 to 5) at the temperature of 30 to 100 ℃. As can be seen from the analysis of the right graph of FIG. 2A (thermogram of entire temperature rise region), the thermal stability of examples 1-5 is substantially the same as that of comparative example 1, but the hydrogel without irradiation (corresponding to comparative example 1) loses more weight in the high temperature region, especially at 450-600 ℃, which indicates that the thermal stability of the hydrogel without irradiation is slightly poor. As can be seen from the analysis of fig. 2B, the weight loss curves of the hydrogels of the examples and comparative examples substantially coincide with the increase in temperature, which indicates that the thermal stability of the irradiated hydrogels (corresponding to examples 6, 8, and 10) is substantially the same as that of the non-irradiated hydrogels (corresponding to comparative example 2). As can be seen from fig. 2C, the hydrogel that was not irradiated (comparative example 4) lost significantly more weight at the same temperature, indicating that the thermal stability of the hydrogel that was not irradiated and to which borax was added was significantly insufficient.
Test example 3:
table 1 shows the results of the measurement of the gel content of the hydrogel. The hydrogels prepared in the examples and comparative examples were weighed and the initial mass m was recorded0Then, the hydrogels prepared in each example and comparative example were put into a bakeDrying in a box until the quality is stable, taking out the hydrogel for weighing, and recording the mass m at the moment1And calculating the water content and the gel content of the hydrogel.
Figure BDA0003120147510000081
Gel content ═ 1-water content (formula 2)
Wherein the level of gel content reflects the degree of crosslinking of the hydrogel. It can be seen that the gel content increased and then decreased with increasing irradiation dose, indicating that the irradiation dose increased the degree of crosslinking. However, too high a dosage may result in degradation of the polymer chains, thereby reducing the gel content. The crosslinking degree is improved, and the structural pores in the hydrogel are increased, so that the ionic conductivity is improved.
TABLE 1 gel content and Water content of hydrogels of examples and comparative examples
Figure BDA0003120147510000082
Figure BDA0003120147510000091
Test example 4:
the ionic conductivity and the electrochemical window were measured at room temperature using the CHI700E series electrochemical workstation. The hydrogels obtained in examples 1, 3, 4, 5 and comparative example 1 were subjected to ion conductivity tests, respectively, as shown in fig. 3A. The hydrogels obtained in example 8 and comparative example 2 were subjected to ion conductivity tests, respectively, as shown in fig. 3B. The hydrogels obtained in example 13 and comparative examples 3 and 4 were subjected to ion conductivity tests, respectively, as shown in fig. 3C.
FIGS. 3A to 3C are graphs showing the ion conductivity analysis of hydrogels obtained in different examples and comparative examples. The abscissa of FIGS. 3A to 3C represents irradiation dose (irradiation dose), the abscissa represents kGy, the ordinate represents ionic conductivity (ionic conductivity), and the ordinate represents mS/cm.
Fig. 3A shows the ionic conductivities of the hydrogels of examples 1, 3, 4, 5 and comparative example 1. The hydrogels of examples 1, 3, 4 and 5 were all prepared after irradiation at doses of 10kGy, 30kGy, 40kGy and 50kGy, respectively, whereas the hydrogel of comparative example 1 was not prepared after irradiation, and zinc sulfate was used in the hydrogels of examples 1, 3, 4, 5 and comparative example 1. As can be seen from fig. 3A, the ion conductivity of the hydrogel after irradiation is significantly increased, and the ion conductivity of the hydrogel is improved by irradiation. Particularly, when the irradiation dose is 30kGy, the ion conductivity of the hydrogel electrolyte is as high as 16.24 mS/cm.
FIG. 3B shows the ionic conductivities of the hydrogels of example 8 and comparative example 2, the hydrogel of example 8 was prepared after irradiation at a dose of 30kGy, the hydrogel of comparative example 2 was not prepared after irradiation, and zinc sulfate and manganese sulfate were used in the hydrogels of example 8 and comparative example 2. As can be seen from the analysis of FIG. 3B, in example 8, the ion conductivity of the hydrogel electrolyte was 3.58mS/cm at an irradiation dose of 30kGy, whereas in comparative example 2, the ion conductivity of the non-irradiated hydrogel was 1.98mS/cm, thus indicating that the ion conductivity of the irradiated hydrogel was significantly increased and that irradiation increased the ion conductivity of the hydrogel.
FIG. 3C shows the ionic conductivities of the hydrogels of example 13 and comparative examples 3 and 4, the hydrogels of example 13 were all prepared after irradiation at a dose of 30kGy, while the hydrogels of comparative examples 3 and 4 were not prepared, wherein the polymer was crosslinked by adding borax in comparative example 4, and zinc sulfate and sodium sulfate were used in the hydrogels of example 13 and comparative examples 3 and 4. Analysis of FIG. 3C reveals that the ion conductivity of the hydrogel electrolyte was 4.87mS/cm at an irradiation dose of 30kGy in example 13, whereas the ion conductivity of the non-irradiated hydrogel was 3.57mS/cm in comparative example 3, thus demonstrating that the ion conductivity of the hydrogel after irradiation increased and irradiation increased the ion conductivity of the hydrogel. The ionic conductivity of example 13 was slightly improved compared to comparative example 4, which used borax as a crosslinking agent, and the ionic conductivity was 4.7mS/cm, but the hydrogel provided in example 13 did not require the addition of additional ingredients, higher ionic conductivity was obtained, and the time period for preparing the hydrogel electrolyte by irradiation was short. Also, it was shown in the above test example 2 that the hydrogel of comparative example 4 was significantly low in thermal stability in the high temperature region of 250 ℃ or more.
FIG. 4 is a graph of electrochemical windows of hydrogels of examples 1, 3, 5 and comparative example 1 provided by the present invention, in which the abscissa of FIG. 4 is potential (potential), the abscissa is unit of V, the ordinate is current (current), and the ordinate is unit of A. The range sizes of the electrochemical windows of the hydrogels obtained in examples 1, 3, 5 and comparative example 1 were observed at the same sweep rate by applying a continuously varying voltage to the hydrogels obtained in examples 1, 3, 5 and comparative example 1. As a result of the test, the zinc deposition peak was not evident in the hydrogel of comparative example 1 which had not been irradiated, but was not evident in the hydrogel of examples 1, 3 and 5 which had been irradiated. Furthermore, the oxygen evolution potential of the hydrogel of comparative example 1 was about 2.35V, whereas the oxygen evolution potential of the hydrogels of examples 1, 3 was about 2.48V, higher than that of comparative example 1, indicating a significant broadening of the voltage window after irradiation. While the oxygen evolution potential of the hydrogel of example 5 was about 2.3V, which correlates with the results of the previous tests, some degradation of the hydrogel was possible due to the higher irradiation dose. The appropriate dose of irradiation can widen the electrochemical window of the hydrogel, so that the electrode material can stably work in the window.
According to the invention, one or two different metal ions are added as hydrogel electrolyte conducting ions, so that the hydrogel electrolyte can be suitable for different water system ion energy storage devices, and therefore, the application range of the hydrogel electrolyte prepared by the method is expanded.
Furthermore, the hydrogel electrolyte disclosed by the invention has more excellent physical and mechanical properties by using polyvinyl alcohol as a matrix of the hydrogel, is prepared by irradiation, widens the electrochemical application window, improves the ionic conductivity, has a wide application range of quasi-solid water-based batteries, and has market application prospects.
Furthermore, the hydrogel electrolyte is prepared by irradiation crosslinking of an electron accelerator, the preparation period is short, the efficiency is high, and additional components such as additional crosslinking agents and initiators are not required to be added, so that the hydrogel electrolyte prepared by the method is low in cost, green and environment-friendly, and convenient to popularize practically and apply on a large scale.
The above description is only a preferred embodiment of the present invention, and is not intended to limit the scope of the present invention, and all modifications and equivalents made by the contents of the present specification and drawings, or directly/indirectly applied to other related technical fields, are included in the scope of the present invention.

Claims (10)

1. A preparation method of a hydrogel electrolyte is characterized by comprising the following steps:
providing an aqueous solution of polyvinyl alcohol;
adding glycerol into the aqueous solution of the metal sulfate, and uniformly mixing;
uniformly mixing a mixed solution of metal sulfate and glycerol with an aqueous solution of polyvinyl alcohol; and
the mixed solution containing the metal sulfate, glycerin and polyvinyl alcohol is irradiated.
2. The method of claim 1, wherein the components are used in amounts, based on the total weight of the hydrogel electrolyte, of:
2-10 wt% of polyvinyl alcohol;
1-5 wt% of glycerol;
2-8 wt% of metal sulfate; and
80-92 wt% of water.
3. The method of claim 1, wherein the irradiation is electron beam irradiation.
4. The method according to claim 3, wherein the electron beam irradiation is performed at a dose of 10 to 50 kGy.
5. The preparation method of claim 2, wherein the polymerization degree of the polyvinyl alcohol is 1700 to 2400, and the alcoholysis degree is 88 to 99%; preferably, the content of the polyvinyl alcohol is in the range of 4-8 wt%.
6. The method according to claim 2, wherein the content of glycerin is in the range of 2 to 4 wt%.
7. The method according to claim 2, wherein the metal sulfate is contained in an amount ranging from 3 to 7 wt%.
8. The method of claim 2, wherein the metal sulfate is one or two selected from the group consisting of zinc sulfate, sodium sulfate, and manganese sulfate.
9. A hydrogel electrolyte obtained by the method for producing a hydrogel electrolyte according to any one of claims 1 to 8.
10. An energy storage device comprising the hydrogel electrolyte of claim 9.
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