CN114421027A - Environment-friendly degradable zinc double-ion battery gel electrolyte, preparation method and application thereof in zinc double-ion battery - Google Patents
Environment-friendly degradable zinc double-ion battery gel electrolyte, preparation method and application thereof in zinc double-ion battery Download PDFInfo
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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
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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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Abstract
An environment-friendly degradable zinc dual-ion battery gel electrolyte, a preparation method and application thereof in a zinc dual-ion battery, belonging to the technical field of zinc dual-ion battery electrolyte preparation. The invention is to add an environmentally friendly hydrophilic polymer to 10M ZnCl2Heating and stirring the solution to obtain uniform and transparent gel stock solution, and drying the gel stock solution to constant weight by a sol-gel method, thereby preparing the novel nontoxic and harmless gel electrolyte with wide working voltage, high ionic conductivity and high water retention; then taking a carbon current collector as a working electrode, a platinum sheet as a counter electrode, an Ag/AgCl electrode as a reference electrode and ZnSO4And carrying out electrodeposition in the aqueous solution to prepare the zinc cathode. Then, the prepared zinc cathode, the gel electrolyte and the carbon current collector anode are assembled into a sandwich structure to prepare the zinc double-ion battery, and the battery is environment-friendly and degradable, has high area capacity and high capacityVoltage window and high cycle stability.
Description
Technical Field
The invention belongs to the technical field of preparation of zinc bi-ion battery electrolytes, and particularly relates to an environment-friendly degradable high-performance zinc bi-ion battery gel electrolyte, a preparation method and application thereof in preparation of a zinc bi-ion battery.
Background
Millions of tons of garbage will be generated each day in the next decade, with the disposable electronic garbage expected to grow exponentially. The energy storage systems in these electronic wastes, such as lithium ion batteries and super capacitors, contain a large amount of heavy metal electrodes and toxic and highly corrosive electrolytes, which pose a serious threat to our living environment. Therefore, recycling and reusing these materials in energy storage systems is critical to sustainable development, and material recycling can be turned off to achieve cyclic economy and carbon neutrality. The challenges here arise from the different requirements for energy storage system electrodes and electrolytes, ranging from non-toxic, high durability and high processability to low cost but completely degradable.
In response to this serious problem, it is urgent to explore the source of the problem by developing an energy storage system using environmentally friendly ions (e.g., H)+、NH4 +、Na+、K+、Zn2+、Al3+) The biodegradable electrode material and the neutral water electrolyte replace strong acid, strong alkali or high-toxicity organic electrolyte. The zinc double-ion battery (ZDIB) combines the advantages of high-energy zinc ion batteries and recyclable carbon-based materials, gets rid of the dependence on toxic elements such as Ni and Co, and attracts wide attention, and the negative ion intercalation is introduced, so that the working voltage is greatly improved. Nevertheless, ZDIB still faces many challenges in application. First, in ZDIB, an environmentally friendly aqueous electrolyte is rarely applied to ZDIB because anions are intercalated into a conventional graphite cathode at a high potential and Oxygen Evolution Reaction (OER) due to a narrow electrochemical window limits the use of high potential cathode materials. Second, Zn2+And anions (diameter
) At the positive electrodeSlow diffusion kinetics in the pores and/or mesopores are responsible for the low capacity, poor rate performance and poor cycling stability of carbon-based ZDIB. Third, although carbon cathodes and zinc ion electrolytes (even safer hydrogel electrolytes) are widely used, ZDIB is discarded in the environment and still difficult to decompose rapidly, possibly leading to the risk of life being taken up by the organism.
Therefore, in order to solve the problem of slow anion intercalation into the positive electrode transport kinetics, it is necessary to develop an ideal electrolyte that allows ZDIB to have higher area capacity and a wider electrochemically stable operating voltage, and to impart full rapid degradation capability to ZDIB, which is the most effective way to solve electronic waste and eliminate battery contamination in the future, but is also challenging.
Disclosure of Invention
In order to overcome the technical defects of the original zinc bi-ion battery and meet the improvement requirement of the original zinc bi-ion battery, the invention provides an environment-friendly degradable high-performance zinc bi-ion battery gel electrolyte, a preparation method and application thereof in preparing the zinc bi-ion battery. Firstly, a high-safety and completely-degradable nontoxic hydrogel electrolyte is constructed, and then an environment-friendly carbon electrode is compounded, so that the zinc double-ion battery with a high potential window and high cycle stability is successfully prepared. Which is an environmentally friendly hydrophilic polymer added to 10M ZnCl2Heating and stirring the solution to obtain uniform and transparent gel stock solution, then pouring the mixed solution into a mould by a sol-gel method, and drying the mixed solution to constant weight, thereby preparing the novel nontoxic harmless gel electrolyte with wide working voltage, high ionic conductivity and high water retention. Then using clean carbon current collector as working electrode, platinum sheet as counter electrode, Ag/AgCl electrode as reference electrode and in ZnSO4Electrodeposition was performed in an aqueous solution, thereby preparing a zinc negative electrode. And then assembling the prepared zinc cathode, the gel electrolyte and the carbon electrode into a sandwich structure to prepare the zinc double-ion battery. The prepared zinc double-ion battery has high area capacity, high voltage window and high cycle stability, and has very wide application prospect.
In order to achieve the purpose, the environment-friendly degradable high-performance zinc dual-ion battery gel electrolyte disclosed by the invention has wide working voltage, high ionic conductivity and high water retention, and the gel electrolyte final product comprises the following components in percentage by mass and 100 percent:
10 to 20 percent of hydrophilic polymer
65 to 75 percent of zinc chloride
10 to 15 percent of water
The invention relates to a preparation method of an environment-friendly degradable high-performance zinc double-ion battery gel electrolyte, which is prepared by mixing a hydrophilic polymer and 2-5 mL of 10M ZnCl2Mixing and stirring the aqueous solution at the temperature of 20-60 ℃ for 2-5 h to obtain a clear and uniform solution; then pouring the solution into a mould (a culture dish with the diameter of 6cm), and drying at 35-45 ℃ to constant weight to obtain a gel electrolyte; the hydrophilic polymer accounts for 10-20 wt% of the gel electrolyte and is reported as GPE-x (x is 10-20).
Preparing a zinc cathode: at a distance of 1.0X 1.0cm2The clean carbon current collector is a working electrode, the platinum sheet is a counter electrode, the Ag/AgCl electrode is a reference electrode, and the concentration of ZnSO is 0.1-0.3M4And carrying out electrodeposition in the aqueous solution at room temperature, controlling the deposition potential to be-0.8V, and continuing for 5-10 minutes, thereby obtaining the zinc cathode on the carbon current collector.
Preparing a double-ion battery: and assembling the positive electrode of the carbon current collector, the gel electrolyte and the zinc negative electrode into a sandwich structure, and flexibly packaging to obtain the zinc double-ion battery.
The hydrophilic polymer is one or more than two of polyvinyl alcohol (PVA) and gelatin (gelatin), but is not limited to the above substances. The carbon current collector is one or two of carbon cloth or carbon paper, but not limited to the above substances.
Drawings
FIG. 1 is an FE-SEM photograph of the gel electrolyte prepared in example 2.
FIG. 2 is a stress-strain curve of the gel electrolytes prepared in examples 1 to 3.
FIG. 3 is a gel electrolysis prepared in examples 1 to 3Proton and 10M ZnCl2Differential thermal scanning analysis curve in the range of-20 to 100 ℃.
FIG. 4 is a graph showing water loss at 40 ℃ for gel electrolytes prepared in examples 1 to 3.
FIG. 5 shows a gel electrolyte prepared in example 2 and 10M ZnCl2The ion conductivity of (a) is plotted as a function of temperature.
Fig. 6 is a polarization curve of the gel electrolyte prepared in example 2 at a direct current voltage.
FIG. 7 shows a gel electrolyte prepared in example 2 and 10M ZnCl2Constant current charging cycle stability curve of (a); the prepared zinc cathode is used as two electrodes, and the current is 0.5mA cm-2。
Fig. 8 is a graph illustrating the manner in which water molecules are bonded in a gel electrolyte. FIG. 8a is 1M ZnCl2、10M ZnCl2And 14 wt% water in the PVA and gelatin mixture; FIG. 8b is a key formation exploration curve of the gel electrolytes prepared in examples 1 to 3.
FIG. 9 shows gel electrolytes and 1M ZnCl prepared in examples 1 to 32、10M ZnCl2Exploration curve of existence form of zinc ion.
Fig. 10 is a graph showing the degradation change of the gel electrolyte prepared in example 2 in water.
FIG. 11 shows a gel electrolyte prepared in example 2 and 10M ZnCl2And graphs showing the results of bacterial growth culture after dilution 10-fold and 100-fold, respectively.
FIG. 12 is a bar graph showing the growth of bacteria after the gel electrolyte, PVA, Gelatin (Gelatin), and 10M zinc chloride solutions prepared in examples 1 to 3 were dissolved and diluted 100-fold respectively and added to the culture medium for colon cancer cells (SW 480).
FIG. 13 shows a gel electrolyte and 10M ZnCl as described in example 52The prepared high-performance zinc double-ion battery has a constant current charging/discharging (GCD) curve in a working voltage range of 0.6-2.0V.
Fig. 14 is a rate performance curve of the environmentally-friendly degradable high-performance zinc bi-ion battery prepared in example 5.
Fig. 15 is a cycle performance curve of the environmentally-friendly degradable high-performance zinc bi-ion battery prepared in example 5.
Detailed Description
The concept and technical effects of the present invention will be clearly and completely described below in conjunction with the embodiments to fully understand the objects, features and effects of the present invention. It is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments, and those skilled in the art can obtain other embodiments without inventive effort based on the embodiments of the present invention, and all embodiments are within the protection scope of the present invention.
Example 1:
mixing polyvinyl alcohol (PVA) with gelatin (gelatin) and ZnCl2The aqueous solution (2mL, 10M) was mixed and stirred at 40 ℃ for 3h to give a clear homogeneous solution. Then pouring the solution into a mould (a culture dish with the diameter of 6cm), and drying at 40 ℃ to constant weight to obtain a gel electrolyte; the hydrophilic polymers polyvinyl alcohol (PVA) and gelatin (gelatin) make up 10 wt% of the total gel electrolyte, with 5 wt% PVA, recorded as GPE-10; the water content was 15.5 wt% and the zinc salt content was 74.5 wt%.
Example 2:
mixing polyvinyl alcohol (PVA) with gelatin (gelatin) and ZnCl2The aqueous solution (2mL, 10M) was mixed and stirred at 40 ℃ for 3h to give a clear homogeneous solution. Then pouring the solution into a mould (culture dish, diameter 6cm), and drying at 40 ℃ to obtain a constant weight gel electrolyte; the hydrophilic polymers polyvinyl alcohol (PVA) and gelatin (gelatin) make up 15 wt% of the total gel electrolyte, with PVA making up 5 wt%, recorded as GPE-15; the water content was 14.7 wt.% and the zinc salt content was 70.3 wt.%.
Example 3:
mixing polyvinyl alcohol (PVA) with gelatin (gelatin) and ZnCl2The aqueous solution (2mL, 10M) was mixed and stirred at 40 ℃ for 3h to give a clear homogeneous solution. Then pouring the solution into a mould (culture dish, diameter 6cm), and drying at 40 ℃ to obtain a constant weight gel electrolyte; the hydrophilic polymers polyvinyl alcohol (PVA) and gelatin (gelatin) make up 20 wt% of the total gel electrolyte, with 5 wt% PVA, recorded as GPE-20; the water content was 14.1wt% by weight, zinc salt content 65.9% by weight
Example 4:
at a distance of 1.0X 1.0cm2Clean carbon cloth current collector as working electrode, platinum sheet as counter electrode, Ag/AgCl electrode as reference electrode, in ZnSO4Electrodeposition was carried out in an aqueous solution (0.2M) at 25 ℃. And controlling the deposition potential to be-0.8V, and preparing the zinc negative electrode (Zn @ CC) on a carbon cloth current collector for 10 minutes.
Example 5:
assembling a carbon cloth anode, the gel electrolyte obtained in the embodiment 1-3) and the zinc cathode obtained in the embodiment 4) into a sandwich structure, and flexibly packaging to prepare the zinc double-ion battery.
Comparative example 1
This comparative example prepared a zinc bi-ion battery, which differed from example 5 in that: the electrolyte adopts 10M ZnCl2The operation was the same as in example 5 except that the aqueous solution was used instead of the gel electrolyte prepared in examples 1 to 3).
The environment-friendly degradable high-performance zinc double-ion battery gel electrolyte synthesized by the invention is subjected to detailed performance characterization, and the specific characterization mode is as follows:
(1) topography analysis
The morphology of the lyophilized gel was observed by using FE-SEM (Hitachi FE-SEM S-4800 instrument).
(2) Infrared spectroscopic analysis
The hydrogel was characterized by infrared spectroscopy (Spectrum FTIR 8400S spectrometer, Shimadzu).
(3) Component content test
Gel electrolyte (GPE) initial weight W0(g) Completely dried in vacuum to constant weight of W1(g) In which PVA, gelatin and ZnCl2There was no loss during heating. The water content (wt%) of the gel electrolyte is calculated by formula (1):
(4) and (3) testing mechanical properties:
the prepared GPE sample was cut into a standard sample bar (length. times. width. times. thickness: 20 mm. times.l 0 mm. times.1 mm), the sample was placed in the center of a plate of a universal material tensile testing machine so as to be kept naturally vertical, and then clamped with a jig at a constant rate (50mm min)-1) And slowly applying the load until the sample bar is broken, measuring the maximum tensile stress strength and the breaking elongation, and calculating corresponding stress and strain data according to the maximum tensile stress strength and the breaking elongation.
(5) Thermal stability test
The gel electrolyte prepared in examples 1 to 3 was mixed with 10M ZnCl2(differential thermal scanning analysis is carried out within the range of-20 to 100 ℃ to observe the change condition.
(6) Determination of the Ionic conductivity
Two platinum sheets were placed on both sides of the gel electrolyte, and ac impedance measurement was performed on an electrochemical workstation, and the change in resistance was observed, and the ionic conductivity (2) was calculated according to the following formula: (R is gel electrolyte resistance, S is gel electrolyte area, L is distance between two platinum sheets)
(7) Electrochemical stability
The gel electrolyte GPE-15 in example 2 was placed under 2V DC voltage for 3000s, and the current change was observed.
(8) Zinc dendrite inhibition capability test
A symmetrical cell was assembled at 0.5mA cm using the zinc negative electrode (Zn @ CC) prepared in example 4-2And then, carrying out constant current circulation performance test and observing the polarization condition of the sample.
(9) Degradable testing
The electrolyte was placed in water, and the disintegration of the electrolyte in water was observed.
(10) Bacterial safety testing
Staphylococcus aureus (s.aureus, BNCC 186335, gram positive) was used as the model microorganism. 10 μ L of Staphylococcus aureus was placed in 10mL Luria-Bertani medium (cyan)Island hopp biotechnology limited), was cultured overnight at 37 ℃ with shaking. Centrifuging at 2000rpm for 10min, collecting bacteria, washing with PBS for 2 times, diluting PBS medium until the Optical Density (OD) of ultraviolet absorption (UV-1800, SHIMADZU) at 600nm is about 0.08-0.1, which is equivalent to bacteria concentration of 108CFU mL-1。
(11) Cell safety test
Taking a culture medium of colon cancer cells (SW480) as an example, PVA, gelatin, zinc chloride and the gel electrolyte prepared in examples 1 to 3 were dissolved, and then proliferation results of the cells after 24 hours of culture by the action of various substances after dilution by 100 times were observed.
(12) Electrochemical testing
The charge and discharge tests, the rate capability tests and the cycle stability tests were performed on Chenghua CHI660E and LANBTS BT-2016S for example 4 and example 5.
And (3) analyzing an experimental result:
the FE-SEM photograph of fig. 1 can clearly observe the porous network structure inside the gel electrolyte in the novel environmentally-friendly and degradable high-performance zinc bi-ion battery prepared in example 2. FIG. a is an FE-SEM photograph of GPE-15 at a scale bar of 50 μm, and FIG. b is an FE-SEM photograph of GPE-15 at a scale bar of 5 μm.
As shown in FIG. 2, it can be seen that the elongation at break of GPE-15 reached 400% and the tensile stress reached 250 kPa. Meanwhile, deformation is gradually reduced along with the increase of the gelatin, and the fracture stress is increased, wherein GPE-15 has the highest fracture stress.
As shown in fig. 3, the peak gradually moves toward the high temperature region as the polymer concentration increases. When the concentration of the polymer reaches 15 wt%, the endothermic peak disappears within the range of-20 to 100 ℃, and the thermodynamically stable water molecules in the GPE are all bound water within the range. However, when the polymer concentration is further increased to 20 wt%, since an excessively high polymer concentration causes excessive polymer-polymer interaction in the system, resulting in ion aggregation, water molecules are not stabilized, and an endothermic peak occurs again at 92 ℃.
As shown in fig. 4, the mass of the electrolyte was maintained above 99% over the storage time of 7 days, especially without any loss of GPE-15, demonstrating that the gel electrolyte had good water retention.
As shown in FIG. 5, the relationship curve of the ion conductivity with the temperature variation conforms to the Arrhenius formula, and at-20 deg.C, the ion conductivity still has a value of 20.8mS cm-1Has an ionic conductivity of 110.2mS cm at 25 DEG C-1The ionic conductivity of (a). In contrast, pure 10M zinc chloride, at 25 ℃ has 34.0mS cm-1The ionic conductivity of (a).
As shown in fig. 6, the gel electrolyte was placed at a direct current voltage of 2V with a platinum sheet as an electrode (both positive and negative electrodes were platinum sheets), and the current was maintained at 0.03mA for 3000 seconds, without any side effect, showing excellent electrochemical stability.
FIG. 7 shows that the current density at 0.5mA cm-2Constant current cycling performance tests were performed and all cells exhibited a small degree of polarization at the initial cycling. The mutation occurred after 310h of the test with 10M zinc chloride, compared to GPE-15 where zinc could be reversibly deposited and stripped within 400 h.
FIG. 8 shows that Fourier transform infrared spectroscopy (FTIR) confirms the O-H content of hydrogen bonds (2,800-3,370 cm)-1) And O-H vibration represents the bonding pattern of water molecules inside GPE, reflecting the chemical environment of hydrogen and oxygen atoms in the different donor (D) -acceptor (A) pairs in FIG. 8. With 1M ZnCl2For reference, the different hydrogen bonding environments of O-H can be divided into four Gaussian peaks for discussion, DAA (3,059cm-1), DDAA (3,224cm-1), DA (3,421 cm-1) respectively-1) And DDA (3,566 cm)-1) Hydrogen bonding. When ZnCl is present2DDAA (3,228 cm) when the solution concentration increased to 10M-1) And DA (3,427 cm)-1) The peaks of (a) are correspondingly increased and shifted, demonstrating that the high concentration of salt occupies the position of the water molecules and that the water molecules are associated together. The hydrogel polymers (PVA and gelatin) and water as a control (water mass fraction of 14%) were considered to be DDAA (3,263 cm)-1) And DA (3,453 cm)-1) The peaks are hydrogen bonding networks formed by O-H, and a red shift of these peaks can still be observed. The DA peak of GPE is obviously enhanced, the DAA peak is obviously weakened and even disappears in GPE-15 and GPE-20, which shows that the polymer matrix successfully stabilizes waterThe activity and free flow of water molecules are greatly reduced. .
FIG. 9 shows when the polymer is added to 10M ZnCl2In (3), the content of water molecules is further reduced. GPE-15 contains only 14 wt% water molecules, but 66 wt% ZnCl2The calculated molar ratio is approximately water: zinc ≈ 2:1, so the form of zinc ion should be present [ Zn (H)2O)6-xClx]2-x. To validate our hypothesis, we tested a series of Raman spectra of GPE at 278cm-1And 397cm-1Near obvious Raman peaks which belong to [ Zn (H) ]2O)6-xClx]2-xAnd Zn (H)2O)6 2+. In 1M ZnCl2In solution, almost all Zn ions are Zn (H)2O)6 2+Exists in a form that the coordination mode of Zn ions gradually changes to [ Zn (H) with the increase of the electrolyte concentration2O)6-xClx]2-x. Hydrophilic hydrogel polymers will exacerbate this trend because the polymers can also form hydrogen bonds with water molecules. It can be found that [ Zn (H) is present in the Raman spectra of GPE-15 and GPE-202O)6-xClx]2-xThe proportion is large, which proves that Zn ions are mainly [ Zn (H) ]2O)6-xClx]2-xExist in the form of (1). As the amount of polymer increases, the amount of water molecules bound to the dissolved Zn ion decreases, eventually forming [ Zn (H)2O)2Cl4]2-And [ ZnCl ]4]2-The ion radius is small, which is beneficial to the insertion of ions into the anode.
As shown in fig. 10, 1g of the gel electrolyte was gradually decomposed in water within 3 hours.
FIG. 11 shows the presence of bacteria in the culture medium (10)7CFU mL-1) Under the action of GPE diluted by 10 times, the GPE can be completely killed within 2h, and the growth of bacteria can be effectively inhibited due to the existence of high salt. Interestingly, when GPE-15 was used diluted 100-fold, bacteria could multiply under the action of GPE due to the lower concentration of effective bactericidal substance of GPE-15. It is worth mentioning that due to the saltHigh concentration, 10 times diluted ZnCl2The solution has good antibacterial effect similar to that of GPE-15 diluted by 10 times. Bacteria in 100-fold diluted 10M ZnCl2The zinc chloride solution can still survive, namely the diluted zinc chloride solution has no harm to microenvironment. Therefore, the raw materials for preparing GPE are nontoxic and harmless to organisms after being diluted for enough times by simulating natural environment.
As shown in FIG. 12, when 10M ZnCl is used2When the cell growth inhibitor is diluted to 100 times of the original concentration, the inhibition effect on cell proliferation is still obvious (the growth rate is only 38.3%). The inhibition of cell proliferation is significantly reduced with increasing polymer content. The growth rate of GPE-20 is 92.2%, and the cell growth rate of GPE-15 is 80.2%, which shows that the polymer effectively reduces the biological toxicity of high-concentration salt to GPE, especially after dilution (simulating that GPE is abandoned in a natural water environment). WiSE in the figure represents high concentration of 10M ZnCl2。
FIG. 13 shows that GPE-15 based zinc bi-ion cells are operated at low current (0.1mA cm)-2～2.0mA cm-2) When discharging, the discharge curve is in a battery type, an obvious discharge platform appears at 1.55V, and Zn @ CC//10M ZnCl2// CC cell (i.e. with Zn @ CC as the negative electrode, 10M ZnCl)2A battery in which CC is the positive electrode as the electrolyte) the same electrochemical behavior is found.
FIG. 14 shows that GPE-15 based zinc bi-ion cells are at 0.1, 0.2, 0.5, 1.0 and 2.0mA cm-2Exhibit 0.27, 0.25, 0.23, 0.21 and 0.20mAh cm at a current density of-2Capacity. When the current returns to 0.1mA cm-2The capacity returns to 0.27mAh cm-2Exhibits good rate performance, while Zn @ CC//10M ZnCl2// CC cell can only recover to 0.23mAh cm-2。
FIG. 15 shows that when the current density was 5mA cm-2In contrast, the capacity retention rate of the GPE-15-based zinc dual-ion battery after 8000 cycles is 96.2 percent2The capacity fade of the/CC cell over 1200 cycles was 85%.
Claims (6)
1. An environment-friendly degradable high-performance zinc bi-ion battery gel electrolyte is characterized in that: calculated by the mass percent and 100 percent, the gel electrolyte final product comprises the following components,
10 to 20 percent of hydrophilic polymer
65 to 75 percent of zinc chloride
10 to 15 percent of water
The hydrophilic polymer is one or two of polyvinyl alcohol and gelatin.
2. The preparation method of the environment-friendly degradable high-performance zinc bi-ion battery gel electrolyte as claimed in claim 1, wherein the preparation method comprises the following steps: is prepared by mixing 2-5 mL of ZnCl with 10M2Mixing and stirring the aqueous solution at the temperature of 20-60 ℃ for 2-5 h to obtain a clear and uniform solution; then drying the solution at 35-45 ℃ to constant weight to obtain a gel electrolyte; the hydrophilic polymer accounts for 10-20 wt% of the gel electrolyte.
3. The use of the environmentally friendly degradable high performance zinc bi-ion battery gel electrolyte of claim 1 in the preparation of a zinc bi-ion battery.
4. The application of the environment-friendly degradable high-performance zinc bi-ion battery gel electrolyte as claimed in claim 3 in the preparation of zinc bi-ion batteries, wherein the gel electrolyte comprises the following components in percentage by weight: the positive electrode of a carbon current collector, a gel electrolyte and a zinc negative electrode are assembled into a sandwich structure, and then flexible packaging is carried out, so that the zinc double-ion battery is prepared.
5. The application of the environment-friendly degradable high-performance zinc bi-ion battery gel electrolyte as claimed in claim 4 in the preparation of zinc bi-ion batteries, wherein the gel electrolyte comprises the following components in percentage by weight: using a clean carbon current collector as a working electrode, a platinum sheet as a counter electrode, an Ag/AgCl electrode as a reference electrode, and adding ZnSO of 0.1-0.3M4Carrying out electrodeposition in water solution at room temperature, controlling the deposition potential at-0.8V for 5-10 minutes, thereby obtainingAnd obtaining the zinc cathode on the carbon current collector.
6. The application of the environment-friendly degradable high-performance zinc bi-ion battery gel electrolyte as claimed in claim 5 in the preparation of zinc bi-ion batteries, wherein the gel electrolyte comprises the following components in percentage by weight: the carbon current collector is one or two of carbon cloth or carbon paper.
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