CN112713293A - High-conductivity gel polymer electrolyte applied to aluminum-air battery and preparation method and application thereof - Google Patents
High-conductivity gel polymer electrolyte applied to aluminum-air battery and preparation method and application thereof Download PDFInfo
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- CN112713293A CN112713293A CN202110094509.7A CN202110094509A CN112713293A CN 112713293 A CN112713293 A CN 112713293A CN 202110094509 A CN202110094509 A CN 202110094509A CN 112713293 A CN112713293 A CN 112713293A
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- 239000005518 polymer electrolyte Substances 0.000 title claims abstract description 62
- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- 239000004372 Polyvinyl alcohol Substances 0.000 claims abstract description 44
- 229920002451 polyvinyl alcohol Polymers 0.000 claims abstract description 44
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims abstract description 36
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims abstract description 33
- 238000003756 stirring Methods 0.000 claims abstract description 19
- ZIUHHBKFKCYYJD-UHFFFAOYSA-N n,n'-methylenebisacrylamide Chemical compound C=CC(=O)NCNC(=O)C=C ZIUHHBKFKCYYJD-UHFFFAOYSA-N 0.000 claims abstract description 15
- 229920000642 polymer Polymers 0.000 claims abstract description 15
- 239000003431 cross linking reagent Substances 0.000 claims abstract description 11
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 28
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- 238000000034 method Methods 0.000 claims description 12
- 229910052782 aluminium Inorganic materials 0.000 claims description 10
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 10
- 239000000843 powder Substances 0.000 claims description 9
- 238000005303 weighing Methods 0.000 claims description 4
- 239000003792 electrolyte Substances 0.000 abstract description 16
- 239000002994 raw material Substances 0.000 abstract description 5
- 150000001875 compounds Chemical class 0.000 abstract description 3
- 229920002635 polyurethane Polymers 0.000 abstract 1
- 239000004814 polyurethane Substances 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 57
- 230000000052 comparative effect Effects 0.000 description 19
- 239000011245 gel electrolyte Substances 0.000 description 16
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 7
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- 239000002184 metal Substances 0.000 description 5
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- 238000010521 absorption reaction Methods 0.000 description 3
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- 238000011160 research Methods 0.000 description 3
- 238000004483 ATR-FTIR spectroscopy Methods 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
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- 239000013078 crystal Substances 0.000 description 2
- 238000002329 infrared spectrum Methods 0.000 description 2
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- 231100000956 nontoxicity Toxicity 0.000 description 2
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- 229920000557 Nafion® Polymers 0.000 description 1
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- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- 239000003990 capacitor Substances 0.000 description 1
- 150000001721 carbon Chemical class 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
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Classifications
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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
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/10—Fuel cells with solid electrolytes
- H01M8/1016—Fuel cells with solid electrolytes characterised by the electrolyte material
- H01M8/1018—Polymeric electrolyte materials
- H01M8/1041—Polymer electrolyte composites, mixtures or blends
- H01M8/1044—Mixtures of polymers, of which at least one is ionically conductive
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F261/00—Macromolecular compounds obtained by polymerising monomers on to polymers of oxygen-containing monomers as defined in group C08F16/00
- C08F261/02—Macromolecular compounds obtained by polymerising monomers on to polymers of oxygen-containing monomers as defined in group C08F16/00 on to polymers of unsaturated alcohols
- C08F261/04—Macromolecular compounds obtained by polymerising monomers on to polymers of oxygen-containing monomers as defined in group C08F16/00 on to polymers of unsaturated alcohols on to polymers of vinyl alcohol
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
- C08F283/06—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polyethers, polyoxymethylenes or polyacetals
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M12/00—Hybrid cells; Manufacture thereof
- H01M12/04—Hybrid cells; Manufacture thereof composed of a half-cell of the fuel-cell type and of a half-cell of the primary-cell type
- H01M12/06—Hybrid cells; Manufacture thereof composed of a half-cell of the fuel-cell type and of a half-cell of the primary-cell type with one metallic and one gaseous electrode
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M12/00—Hybrid cells; Manufacture thereof
- H01M12/08—Hybrid cells; Manufacture thereof composed of a half-cell of a fuel-cell type and a half-cell of the secondary-cell type
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/10—Fuel cells with solid electrolytes
-
- 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
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
Abstract
The invention relates to a preparation method of a high-conductivity alkaline gel polymer electrolyte, which comprises the steps of mixing and stirring a polyvinyl alcohol solution and a polyethylene oxide solution to obtain a uniform and stable polymer solution; then adding the N, N' -methylene bisacrylamide crosslinking agent solution and the potassium hydroxide solution, and uniformly mixing to obtain the modified polyurethane. The gel polymer of the inventionThe compound electrolyte is a three-dimensional network structure which has an amorphous structure, high thermal stability, high water retention and transparency and certain deformation capacity and is formed by polyvinyl alcohol and polyethylene oxide under the action of a cross-linking agent N, N' -methylene bisacrylamide, and the electric conductivity can be stably maintained at 0.199S cm‑1About 43.3 mW/cm in power density‑2The requirements of the metal-air battery can be met; the electrolyte has the advantages of simple preparation process, low cost, low price of the used raw materials and easy obtainment.
Description
Technical Field
The invention belongs to the technical field of aluminum-air batteries, and relates to a high-conductivity alkaline gel polymer electrolyte prepared from polyvinyl alcohol, polyethylene oxide and N, N' -methylene bisacrylamide, and a preparation method and application thereof.
Background
The aluminum-air battery has higher theoretical energy density (8100 Wh kg)-1) The advantages of light weight of metal aluminum, rich raw materials, long service life of the battery, no toxicity, harmlessness, environmental friendliness and the like are widely researched, but the electrolyte of the liquid aluminum-air battery is easy to leak and has a safety problem, and the working performance of the battery is greatly influenced due to the severe self-corrosion of metal in an alkaline solution.
In recent years, Gel Polymer Electrolytes (GPEs) have been a hot point of research as a novel electrolyte because they have advantages such as good mechanical properties and thermal stability, high specific energy, and reduced leakage of the electrolyte compared to a liquid electrolyte. Yang et al applied polyvinyl alcohol (PVA) and polyacrylic acid (PAA) to aluminum air batteries, Romero et al applied polyvinyl alcohol (PVA) to zinc air batteries, and many have conducted extensive studies on the application of polymer electrolytes to metal air batteries.
The gel polymer electrolyte forms a network frame by a polymer, the liquid electrolyte flows in the frame, the gel polymer electrolyte solves the problems of electrolyte leakage and anode corrosion of the existing metal-air battery, and the alkaline gel polymer electrolyte has higher room-temperature conductivity (the room-temperature conductivity is generally 10)-3～10-2S/cm-1The method has the characteristics of simple preparation process, rich raw materials, convenient carrying of the battery, high safety and stability and the like, and has great research significance in the aspects of metal air batteries, super capacitors and the like.
The alkaline gel polymer electrolyte mainly comprises: polyethylene oxide (PEO), polyvinyl alcohol (PVA), and polyacrylic acid (PAA). The PEO-based polymer electrolyte has good mechanical properties, but high crystallinity, resulting in low room temperature conductivity, about 1X 10-3 S cm-1It is difficult to meet the requirements of practical battery electrolytes (up to 10)-3S/cm-1Above). The PVA-based polymer electrolyte has excellent chemical stability, electrochemical inertness, durability, nontoxicity, simple preparation and higher ionic conductivity of about 1 × 10-2S cm-1And thus, it is a hot spot in the research direction of polymer electrolytes. The PAA-based alkaline polymer electrolyte has the highest conductivity of about 1 × 10-1S cm-1However, they are inferior in mechanical strength and expensive, and are greatly hindered from practical use.
The metal-air battery taking the gel polymer as the electrolyte is developed in the directions of outdoor communication, health monitoring, field trip, military equipment and the like as wearable electronic equipment, the use condition is more complex, and the requirements on the electrolyte such as safety, circulation stability and the like are met, and higher requirements on conductivity and power density are also met. And the gel polymer electrolyte has low porosity due to the formed network frame, so that a large amount of alkaline electrolyte is difficult to absorb, and the conductivity and power density of the metal-air battery are not high. The current methods for solving such problems are: adding inorganic matters to construct a network frame; adding pore-forming agent to increase the porosity of the electrolyte; a series of methods such as adding a corrosion inhibitor and inhibiting the self-corrosion of metal are used for improving the electrochemical performance of the metal-air battery, but the methods are relatively complex in process and relatively high in preparation cost.
Disclosure of Invention
Aiming at the problems in the prior art, the invention aims to provide a high-conductivity alkaline gel polymer electrolyte applied to an aluminum-air battery, which has the advantages of high water retention, high transparency, high conductivity, high power density and the like, and the electrolyte has the advantages of low price of raw materials and simple preparation process.
The invention also provides a preparation method of the high-conductivity alkaline gel polymer electrolyte and application of the high-conductivity alkaline gel polymer electrolyte in an aluminum air battery.
In order to achieve the purpose, the invention adopts the following technical scheme:
a preparation method of a high-conductivity alkaline gel polymer electrolyte comprises the following steps:
1) mixing and stirring a polyvinyl alcohol solution and a polyethylene oxide solution to obtain a uniform and stable polymer solution;
2) adding a cross-linking agent solution and a potassium hydroxide solution into the polymer solution obtained in the step 1), and uniformly mixing to obtain the alkaline gel polymer electrolyte.
Specifically, the crosslinking agent is preferably N, N' -methylenebisacrylamide.
Further, the mass ratio of the polyvinyl alcohol to the polyethylene oxide to the N, N' -methylene bisacrylamide is 64-100: 64-100: 12.
further, in the alkaline gel polymer electrolyte obtained in the step 2), the mass concentration of polyvinyl alcohol is 3.6-5.5%, the mass concentration of polyethylene oxide is 3.6-5.5%, and the molar concentration of potassium hydroxide is 0.8-1.2 mol/L.
Further, the step 1) is specifically as follows: weighing a certain amount of polyvinyl alcohol powder, adding the polyvinyl alcohol powder into deionized water at room temperature (25 ℃), then magnetically stirring the polyvinyl alcohol powder in a water bath kettle for 0.1 to 1 hour, and gradually increasing the temperature of the water bath kettle to 80 to 90 ℃ to obtain a stable solution A; weighing a certain amount of polyethylene oxide powder, and magnetically stirring for about 1h at room temperature (25 ℃) to uniformly disperse the polyethylene oxide powder in deionized water to obtain a stable solution B; pouring the solution B into the solution A, and continuously stirring in a water bath kettle to obtain a uniform and stable polymer solution.
The invention provides the high-conductivity alkaline gel polymer electrolyte prepared by the preparation method.
The invention also provides application of the high-conductivity alkaline gel polymer electrolyte in preparation of an aluminum air battery.
Compared with the prior art, the invention has the following beneficial effects:
1) the invention selects N, N '-methylene bisacrylamide as a cross-linking agent, so that polyvinyl alcohol, polyethylene oxide and N, N' -methylene bisacrylamide form a three-dimensional network structure with an amorphous structure, high thermal stability, high water retention and transparency and certain deformation capacity, and the mechanical property, the conductivity and the power density of the alkaline gel polymer electrolyte are improved through the network structure; the conductivity can be stably maintained at 0.199S cm-1About 43.3 mW/cm in power density-2The requirements of the metal-air battery can be met;
2) the preparation process of the gel polymer electrolyte is simple, the cost is low, and the used raw materials are low in price and easy to obtain. The gel polymer electrolyte prepared by the method has a stable structure and certain flexibility, and can meet the requirements of wearable energy storage equipment; the network structure is stable, and the electrochemical performance is excellent.
Drawings
FIG. 1 is a graph comparing X-ray diffraction (XRD) patterns of gel polymer electrolytes prepared in example 1 of the present invention and comparative example 3;
FIG. 2 is a graph comparing infrared spectra (ATR-FTIR) of gel polymer electrolytes prepared in example 1 of the present invention and comparative example 2;
FIG. 3 is a graph comparing impedance (EIS) of gel polymer electrolytes prepared in example 1 of the present invention and comparative example 1;
FIG. 4 is a graph of Open Circuit Potential (OCP) of an aluminum-air battery assembled from the gel polymer electrolyte prepared in example 1 of the present invention;
FIG. 5 is a graph showing the results of linear voltammetric scanning (LSV) of an aluminum-air cell assembled from the gel polymer electrolyte prepared in comparative example 1 of the present invention;
fig. 6 is a graph showing the results of linear voltammetry scans (LSVs) of an aluminum-air cell assembled from the gel polymer electrolyte prepared in example 1 of the present invention;
FIG. 7 is a graph showing the discharge characteristics of an aluminum-air battery assembled with the gel polymer electrolytes prepared in example 1 of the present invention and comparative example 2.
Detailed Description
The technical solution of the present invention is further described in detail with reference to the following examples, but the scope of the present invention is not limited thereto.
The reagents and starting materials used in the following examples are all conventional materials available on the market.
Example 1
A preparation method of a high-conductivity alkaline gel polymer electrolyte specifically comprises the following steps:
1) 2 g of polyvinyl alcohol (molecular weight: 205000) is weighed and added into 14 mL of deionized water under the condition of room temperature (25 ℃), then the mixture is magnetically stirred in a water bath kettle and is continuously stirred for about 1h, meanwhile, the temperature of the water bath kettle is gradually increased to 85 ℃ until the mixture is completely dissolved to obtain a PVA solution (a layer of film is prevented from being formed on the surface of the PVA solution when the mixture is constantly observed in the stirring process), and finally the PVA solution is in a milky foam shape. Similarly, 2 g of polyethylene oxide (molecular weight 300000) was added to 14 mL of deionized water and magnetically stirred at room temperature for about 1h to dissolve it sufficiently to give a paste, resulting in a PEO solution. Slowly adding the fully dissolved PEO solution into the PVA solution which is magnetically stirred at the temperature of 85 ℃, and continuously stirring for about 1 hour to ensure that the PEO solution is completely dissolved and is viscous paste to obtain a polymer solution;
2) dropwise adding a prepared N, N' -Methylene Bisacrylamide (MBA) cross-linking agent solution (the cross-linking agent solution is formed by dissolving 0.3 g of MBA in 5 mL of deionized water at normal temperature) into the polymer solution obtained in the step 1), finally dropwise adding 5 mL of 7M/L KOH solution, fully stirring, and stirring for about 20 min to find that the solution becomes a gel state, thereby obtaining the alkaline gel polymer electrolyte.
Aluminum air cell performance test
The alkaline gel polymer electrolyte prepared in example 1 was cut into a circular gel electrolyte having a thickness of 3 mm and a diameter of 2 cm, and an aluminum foil having a thickness of 0.1 mm was used as an anode, followed by a catalyst-coated waterproof carbon cloth (1 x1 cm)2，1.97 mg/cm2) And respectively placing the air cathode and the gel electrolyte on two sides of the prepared gel electrolyte, and assembling the gel electrolyte and the gel electrolyte into the gel aluminum air battery by using a plastic mould (PVC). The open-circuit potential test of the battery is carried out under the following test conditions: the scanning speed was 0.01 v/s and the scanning time was 120 s. The power density of the cell was tested under conditions of an initial voltage of 1.5 v and a sweep rate of 0.01 v/s.
The preparation method of the air cathode comprises the following steps:
dissolving 5mg of catalyst in a mixed solution composed of 250uL deionized water, 250uL ethanol and 70uL Nafion, performing ultrasonic treatment for 30 min to uniformly disperse the catalyst, sucking the mixed solution of 225uL (1.97mg) and uniformly coating the mixed solution on a substrate with the thickness of 1x1 cm2The waterproof carbon cloth is placed in a drying oven at 60 ℃, and the sample is completely dried after about 40min to obtain the waterproof carbon cloth. Waterproof carbon cloth was purchased from Taiwan carbon technologies, Inc. (model number WOS 1002/1009); the catalyst is a refined carbon Mn-based modified carbon catalyst, and is purchased from green original activated carbon Co., Ltd (model TN/MC-Z313, load type: Mn composite oxide).
The alkaline gel polymer electrolyte prepared in example 1 was cut into a circular gel electrolyte having a thickness of 2 mm and a diameter of 0.8 cm, sandwiched between two circular stainless steel sheets, using a CHI760E electrochemical workstation, under the test conditions: the scanning frequency is (1-10)6Hz) and voltage of 0 v, and impedance values of the gel electrolyte were obtained. According to the formula: σ = l/RbA (l means the thickness of the gel electrolyte, RbIs the impedance value of the gel electrolyte tested by the electrochemical workstation, and a is the area of the gel electrolyte), and the conductivity of the gel electrolyte is calculated.
The alkaline gel polymer electrolyte prepared in example 1 was cut into a circular gel electrolyte having a thickness of 3 mm and a diameter of 2 cm, and an aluminum plate having a thickness of 5 mm was used as an anode to coat a catalystWaterproof carbon cloth (1 x1 cm)2，1.97 mg/cm2) And respectively placing the air cathode and the gel electrolyte on two sides of the prepared gel electrolyte, and assembling the gel electrolyte and the gel electrolyte into the gel aluminum air battery by using a plastic mould (PVC). The cell was placed at 1 mA/cm2The discharge test is carried out under the current density to obtain a stable discharge platform and effective working time of the battery.
The X-ray diffraction (XRD) results of the alkaline gel polymer electrolyte prepared in example 1 above are shown in fig. 1, which shows that it is in an amorphous state, resulting in an increase in the conductivity of the electrolyte. From the impedance (EIS) plot of FIG. 3, the conductivity can be calculated to be about 0.199S cm-1Fig. 4 is an open circuit voltage assembled into an aluminum-air cell, which is relatively stable and about 1.6V, and the linear voltammetric scan (LSV) results of fig. 6 show that: the power density of the aluminum-air battery is 43.3 mW cm-2. As can be seen from FIG. 7, at 1mA cm-2The aluminum-air battery can discharge stably for 9.7h at the current density of (2). Thus illustrating that: the alkaline gel polymer electrolyte prepared by the invention has excellent electrochemical performance.
Comparative example 1
The preparation method of the alkaline gel polymer electrolyte comprises the following steps:
1.6g of polyvinyl alcohol (molecular weight 205,000) is weighed and added into 14 mL of deionized water at room temperature (25 ℃), then the mixture is magnetically stirred in a water bath kettle, the stirring is continued for about 1h, meanwhile, the temperature of the water bath kettle is gradually increased to 80 ℃ until the mixture is completely dissolved to obtain a PVA solution (a layer of film is prevented from being formed on the surface of the solution when the stirring process is carried out), and finally the solution is in a milky foam shape. Similarly, 2 g of polyethylene oxide (molecular weight 300,000) was added to 14 mL of deionized water and magnetically stirred at room temperature for about 1h to dissolve it sufficiently to give a paste, resulting in a PEO solution. And slowly adding the PEO solution which is fully dissolved into the PVA solution which is magnetically stirred at the temperature of 80 ℃, and continuously stirring for about 1 hour to ensure that the PEO solution is completely dissolved and is viscous paste to obtain the polymer solution. Finally, 5 mL of 7M/L KOH solution is added dropwise, the mixture is fully stirred for about 30 min to obtain a uniform and transparent solution, and the solution is poured into a culture dish and is kept stand at room temperature overnight to obtain the alkaline gel polymer electrolyte.
FIG. 3 is a graph showing the impedance (EIS) comparison of the polymer electrolytes of example 1 and comparative example 1, from which it can be calculated that the conductivity of the polymer electrolyte of comparative example 1 is about 0.077S cm-1An order of magnitude difference compared to example 1, fig. 5 and 6 are graphs of the results of linear voltammetric scans (LSV) of comparative example 1 and example 1, respectively, 43.3 mW cm from example 1-2In contrast, comparative example 1, the polymer electrolyte had a power density of about 26.5 mW cm-2The electrochemical performance has a large gap.
Comparative example 2
The preparation method of the alkaline gel polymer electrolyte comprises the following steps:
2 g of polyvinyl alcohol (molecular weight 205,000) is weighed and added into 14 mL of deionized water at room temperature (25 ℃), then the mixture is magnetically stirred in a water bath kettle, the stirring is continued for about 1h, meanwhile, the temperature of the water bath kettle is gradually increased to 85 ℃ until the mixture is completely dissolved to obtain a PVA solution (a layer of film is prevented from being formed on the surface of the PVA solution when the mixture is constantly stirred), and finally the PVA solution is in a milky foam shape. Similarly, 2 g of polyethylene oxide (molecular weight 300,000) was added to 14 mL of deionized water and magnetically stirred at room temperature for about 1h to dissolve it sufficiently to give a paste, resulting in a PEO solution. And slowly adding the PEO solution which is fully dissolved into the PVA solution which is magnetically stirred at the temperature of 85 ℃, and continuously stirring for about 1 hour to ensure that the PEO solution is completely dissolved and is viscous paste to obtain the polymer solution. Finally, 5 mL of 7M/L KOH solution is added dropwise, the mixture is fully stirred for about 30 min to obtain a uniform and transparent solution, and the solution is poured into a culture dish and is kept stand at room temperature overnight to obtain the alkaline gel polymer electrolyte.
The infrared spectrum (ATR-FTIR) of the alkaline gel polymer electrolyte obtained in example 1 and comparative example 2 is shown in FIG. 2. As can be seen from FIG. 2, 3410 cm-1The stretching of-OH is shown, the width of the absorption peak of the comparative example 2 is small, and the addition of the cross-linking agent N, N' -Methylene Bisacrylamide (MBA) leads the molecular main chain of the polyvinyl alcohol and the polyethylene oxide to be combined with more-OH to form a large number of hydrogen bridges, thereby being beneficial to the storage of the electrolyte and improving the electrochemistry of the gel electrolyteEnergy is saved; 2961 cm-1Where is the tensile vibration of the C-H bond, the absorption peak of comparative example 2 is stronger than that of example 1, 1435 cm-1The peak is-CH bent, and the absorption peak of comparative example 2 is weaker than that of example 1, which shows that the addition of the crosslinking agent N, N' -Methylene Bisacrylamide (MBA) causes great deformation of the molecular main chains of the polyvinyl alcohol and the polyethylene oxide, forms a complex and stable network framework and has good thermal stability. From FIG. 7, it can be seen that comparative example 2 is at 1mA cm-2The aluminum-air battery can stably discharge for about 5.1 h at the current density of (3). Thus illustrating that: the alkaline gel polymer electrolyte prepared by the invention has excellent electrochemical performance.
Comparative example 3
The preparation method of the alkaline gel polymer electrolyte comprises the following steps:
2 g of polyvinyl alcohol (molecular weight 205,000) is weighed and added into 14 mL of deionized water at room temperature (25 ℃), then the mixture is magnetically stirred in a water bath kettle, the stirring is continued for about 1h, meanwhile, the temperature of the water bath kettle is gradually increased to 90 ℃ until the mixture is completely dissolved to obtain a PVA solution (a layer of film is prevented from being formed on the surface of the PVA solution when the mixture is constantly stirred), and finally the PVA solution is in a milky foam shape. Similarly, 1.6g of polyethylene oxide (molecular weight 300,000) was added to 14 mL of deionized water and magnetically stirred at room temperature for about 1h to dissolve it sufficiently to give a paste, resulting in a PEO solution. And slowly adding the PEO solution which is fully dissolved into the PVA solution which is magnetically stirred at the temperature of 90 ℃, and continuously stirring for about 1 hour to ensure that the PEO solution is completely dissolved and is viscous paste to obtain the polymer solution. Finally, 5 mL of 7M/L KOH solution is added dropwise, the mixture is fully stirred for about 30 min to obtain a uniform and transparent solution, and the solution is poured into a culture dish and is kept stand at room temperature overnight to obtain the alkaline gel polymer electrolyte.
Fig. 1 is an X-ray diffraction (XRD) comparison graph of the alkaline gel polymer electrolytes prepared in example 1 and comparative example 3, and comparative example 3 exhibits a certain crystalline state, which is a characteristic peak of KOH at 2 θ =32.1 °, indicating that there is a certain crystal present, but most of it appears amorphous with polyvinyl alcohol and polyethylene oxide at 2 θ =14.5 ° and 2 θ =16.3 °, with polyvinyl alcohol and polyethylene oxideThe characteristic peaks of the ethylene oxide do not correspond to each other, and are presumed to be the characteristic peak of a salt formed by complexing the ethylene oxide and KOH after the ethylene oxide and the KOH are compounded or the radial diffraction peak of a compound product of the ethylene oxide and the KOH, and the electric conductivity of the electrolyte is not higher than about 0.066S cm due to the existence of the crystal structure of the compound product-1Much lower than the conductivity of the electrolyte of example 1, 0.199S cm-1Thus, it is stated that: the alkaline gel polymer electrolyte prepared by the invention has excellent electrochemical performance.
The foregoing shows and describes the general principles and features of the present invention, together with the advantages thereof. It will be understood by those skilled in the art that the present invention is not limited to the embodiments described above, which are described in the specification and illustrated only to illustrate the principle of the present invention, but that various changes and modifications may be made therein without departing from the spirit and scope of the present invention, which fall within the scope of the invention as claimed. The scope of the invention is defined by the appended claims and equivalents thereof.
Claims (7)
1. The preparation method of the high-conductivity alkaline gel polymer electrolyte is characterized by comprising the following steps of:
1) mixing and stirring a polyvinyl alcohol solution and a polyethylene oxide solution to obtain a uniform and stable polymer solution;
2) adding a cross-linking agent solution and a potassium hydroxide solution into the polymer solution obtained in the step 1), and uniformly mixing to obtain the alkaline gel polymer electrolyte.
2. The method for preparing a highly conductive alkaline gel polymer electrolyte as claimed in claim 1, wherein the crosslinking agent is N, N' -methylenebisacrylamide.
3. The preparation method of the high-conductivity alkaline gel polymer electrolyte according to claim 1, wherein the mass ratio of the polyvinyl alcohol to the polyethylene oxide to the N, N' -methylenebisacrylamide is 64-100: 64-100: 12.
4. the method for preparing the high-conductivity alkaline gel polymer electrolyte according to claim 3, wherein the mass concentration of the polyvinyl alcohol in the alkaline gel polymer electrolyte obtained in the step 2) is 3.6-5.5%, the mass concentration of the polyethylene oxide is 3.6-5.5%, and the molar concentration of the potassium hydroxide is 0.8-1.2 mol/L.
5. The method for preparing the high-conductivity alkaline gel polymer electrolyte according to claim 1, wherein the step 1) is specifically: weighing a certain amount of polyvinyl alcohol powder, adding the polyvinyl alcohol powder into deionized water at room temperature, magnetically stirring the mixture in a water bath kettle for 0.1 to 1 hour, and gradually increasing the temperature of the water bath kettle to 80 to 90 ℃ to obtain a stable solution A; weighing a certain amount of polyethylene oxide powder, and uniformly dispersing the polyethylene oxide powder in deionized water at room temperature to obtain a stable solution B; pouring the solution B into the solution A, and continuously stirring in a water bath kettle to obtain a uniform and stable polymer solution.
6. The highly conductive alkaline gel polymer electrolyte prepared by the method of any one of claims 1 to 5.
7. Use of the high-conductivity alkaline gel polymer electrolyte as claimed in claim 6 for the preparation of an aluminum air battery.
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| CN114725585A (en) * | 2022-04-29 | 2022-07-08 | 星铝新能源科技(徐州)有限公司 | Aluminum-air battery and electrolyte thereof |
| CN117039075A (en) * | 2023-06-16 | 2023-11-10 | 江苏微道能源科技有限公司 | Alkaline gel electrolyte membrane with high tensile strength and strong water retention, and preparation method and application thereof |
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