CN116093426A - Electropolymerized gel electrolyte battery and preparation method thereof - Google Patents

Electropolymerized gel electrolyte battery and preparation method thereof Download PDF

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CN116093426A
CN116093426A CN202310127663.9A CN202310127663A CN116093426A CN 116093426 A CN116093426 A CN 116093426A CN 202310127663 A CN202310127663 A CN 202310127663A CN 116093426 A CN116093426 A CN 116093426A
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gel
gel electrolyte
battery
electropolymerized
precursor solution
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杨培华
陈良源
刘抗
陈鹏博
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Wuhan University WHU
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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
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
    • H01M10/0565—Polymeric materials, e.g. gel-type or solid-type
    • 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
    • H01M10/05—Accumulators with non-aqueous electrolyte
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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
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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
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Abstract

The invention provides an electropolymerized gel electrolyte battery, which comprises a negative electrode, a positive electrode and a gel electrolyte; the negative electrode is a metal electrode; the gel electrolyte is prepared by in-situ polymerization of gel precursor solution infiltrated into a diaphragm in a battery through electric signal treatment; the gel precursor solution includes an anionic polymer monomer and a crosslinking agent. The invention also provides a preparation method of the electropolymerized gel electrolyte battery. Compared with common photo-polymerization and thermal-polymerization gel, the prepared electro-polymerization ionic gel does not need to add a free radical initiator, and the ionic gel prepared by in-situ polymerization in the battery does not agglomerate and is uniformly deposited on the rough electrode surface, so that compared with the ultraviolet-polymerization gel electrolyte prepared outside, the prepared electro-polymerization ionic gel can obviously reduce the impedance of an electrode interface and the gel electrolyte and improve the bonding force between the electrode interface and the gel electrolyte. Cell performance tests show that cells containing electropolymerized gel electrolytes have longer cycle life, better rate capability and cycle performance of the cells.

Description

Electropolymerized gel electrolyte battery and preparation method thereof
Technical Field
The invention belongs to the technical field of metal ion batteries, and particularly relates to an electropolymerized gel electrolyte battery and a preparation method of the electropolymerized gel electrolyte battery.
Background
The gel electrolyte has the characteristics of solid cohesion and liquid diffusivity, along with the development of the secondary battery, the gel electrolyte not only can meet the requirements of the metal ion battery on electrochemical performance and reduce the safety problem caused by an organic solvent, but also has the characteristics of flexibility, excellent interface contact and the like, and is considered by numerous researches to be the development direction of next-generation high-performance electrolyte, and is the electrolyte most likely to replace organic electrolyte. However, in the current commonly used gel polymer metal secondary battery system, the most commonly used external ultraviolet light initiated photopolymerization and thermal initiated polymerization are complicated in steps for obtaining the gel electrolyte in an ex-situ polymerization mode, and more organic solvent is required to be consumed, so that environmental pollution is easily caused in the later solvent recovery process. Meanwhile, in the battery assembled by the gel electrolyte prepared by the two external transfer methods, the gel electrolyte/electrode interface compatibility is poor, and the overall performance of the battery is seriously affected due to the existence of larger interface impedance.
While in situ gel electrolyte preparation strategies are indeed effective, they require relatively harsh reaction conditions, including toxic reagents, high temperature or ultraviolet radiation. At present, most of the methods for preparing metal secondary battery in-situ polyelectrolyte are to make precursor solution initiate monomer molecule polymerization on the surface of electrode in situ, gel and assemble the battery, thus obtaining gel polymer electrolyte capable of conducting metal ions. There have been few studies to initiate the polymerization of monomer molecules in situ in assembled cells, which require the addition of a thermal initiator and by means of heat promote chemical crosslinking of the monomer within the cell. Therefore, both of the above-mentioned conventional in-situ polymerization methods cannot effectively simplify the formulation and the preparation and assembly process of the battery.
Based on the above, a brand-new preparation method of the gel electrolyte is provided, and on the basis of simplifying the formulation of the gel precursor solution and the preparation and assembly process of the battery, the cycle performance and the rate performance of the gel electrolyte battery are improved, so that the technical problem to be solved is needed.
Disclosure of Invention
An object of the present invention is to provide a gel electrolyte battery having high cycle performance and capacity retention.
The second object of the present invention is to provide a method for preparing an electropolymerized gel electrolyte cell capable of simplifying the formulation of a gel precursor solution and the process of preparing and assembling the cell.
One of the achievement purposes of the invention adopts the technical proposal that: providing an electropolymerized gel electrolyte cell comprising a negative electrode, a positive electrode, and a gel electrolyte;
the negative electrode is a metal electrode; the gel electrolyte is prepared by in-situ polymerization of gel precursor solution infiltrated into a diaphragm in a battery through electric signal treatment; the gel precursor solution includes an anionic polymer monomer and a crosslinking agent.
Aiming at the problems existing in the prior art, the invention provides a technical scheme for obtaining carbonyl free radicals by an electrochemical method, and using the electropolymerization process for in-situ preparation of gel electrolyte in a battery, and realizing double simplification of a gel precursor solution formula and a battery preparation and assembly process.
In the electropolymerized gel electrolyte battery provided by the invention, the gel electrolyte is a quasi-solid structure of polymer network gel and glass fiber membrane formed by immersing the glass fiber membrane in anionic polymer monomer/cross-linking agent precursor solution and assembling the battery under the treatment of various electric signals. Because a plurality of monomer molecules contain N, O and other atoms capable of providing lone pair electrons or pi bonds containing a plurality of delocalized electrons, in the gel forming process, the surface of a metal electrode and a precursor solution generate a charge transfer process, a gel electrolyte is fully contacted with an interface, and electrode metal ions accept more lone pair electrons or a plurality of delocalized electrons to form more coordination bonds which enable the metal electrode and the precursor solution to be combined. The electrolyte is favorable for improving ionic conductivity, reducing the impedance of an electrode interface and a gel electrolyte and improving the binding force between the electrode interface and the gel electrolyte, and can also improve the structural stability of the anode and cathode materials in the charge and discharge process, so that the electrolyte can be widely applied to various irregular surfaces and bending scenes.
The second technical scheme adopted for realizing the purpose of the invention is as follows: provided is a method for preparing an electropolymerized gel electrolyte cell, comprising the steps of:
s1, preparing gel precursor solution containing anionic polymer monomers and a cross-linking agent;
s2, infiltrating the gel precursor solution into a glass fiber diaphragm to obtain an infiltrated diaphragm;
s3, assembling the infiltrated diaphragm, the anode and the metal cathode into a battery, and carrying out in-situ polymerization on the gel precursor solution in the battery to form a gel electrolyte under the treatment of an electric signal, so as to obtain the electropolymerized gel electrolyte battery.
In step S1, the gel precursor solution is prepared from 20 to 40wt.% of ionic gel monomer, 0.4 to 1.0wt.% of cross-linking agent, and the balance of water or organic solvent.
Further, the anionic polymer monomer is selected from one or more of 2-acrylamido-2-methylpropanesulfonic acid sodium salt, 2-acrylamido-2-methylpropanesulfonic acid zinc salt, acrylic acid sodium salt, methacrylic acid sodium salt, ethylene sulfonic acid sodium salt, styrene sulfonic acid sodium salt and p-vinylbenzene sulfonic acid sodium salt.
In the present invention, an ion gel electrolyte, zn, is used 2+ 、Li + 、Na + And Al 3+ The plasma cation can be selected according to the working requirement of the electrode without adding Cl - 、ClO 4 - 、NO 3 - And SO 4 2- The metal salt of the plasma effectively reduces the generation of byproducts.
Further, the cross-linking agent is selected from one or more of N, N' -methylenebisacrylamide and derivatives thereof or ethylene glycol dimethacrylate and derivatives thereof.
Further, in the step S2, the thickness of the glass fiber diaphragm is 1-1.2 mm, and the aperture is 2.5-3.0 μm; the volume of the gel precursor solution accounts for 40-50% of the volume of the glass fiber diaphragm.
In the invention, the ionic gel precursor solution is immersed into the glass fiber diaphragm, and a polymer network gel and a quasi-solid state of the glass fiber diaphragm are formed under the treatment of an electric signal. The gel electrolyte polyanion network structure can effectively improve the migration number of cations, is beneficial to improving the performance of the metal ion battery, can improve the deposition uniformity of metal ions in the charging process, and better inhibits the growth of negative dendrites.
Preferably, after step S2, the infiltrated membrane is placed in a dark, low temperature environment for 0.5-2 hours, and the gel precursor solution is fully infiltrated into the glass fiber membrane and air in the membrane is expelled by adopting a vacuum, pressurizing or alternating vacuum-pressurizing circulation mode.
Further, in the step S3, the metal of the metal negative electrode of the battery is selected from one of zinc, lithium, sodium, and aluminum.
Further, in the step S3, the positive electrode material of the battery includes a metal oxide or prussian blue and derivatives thereof; the metal oxide is selected from one of manganese oxide, titanium oxide, iron oxide and vanadium oxide.
Preferably, the preparation process of the positive electrode plate of the battery is as follows: uniformly mixing a uniformly ground positive electrode material, acetylene black and polyvinylidene fluoride (PVDF) dissolved in N-methyl pyrrolidone to form slurry, coating the slurry on a titanium foil with the thickness of 20 mu m, drying the titanium foil at 80 ℃ for 12 hours to obtain a positive electrode plate, wherein the mass ratio of the positive electrode material to the acetylene black to the polyvinylidene fluoride is 8: (1-2): (1-2).
Further, in the step S3, the battery assembling method is as follows: and placing the electrode plates into a battery shell, placing a soaked glass fiber diaphragm between the positive electrode plate and the negative electrode plate for separation, and then packaging the battery to obtain the metal ion battery.
Preferably, in the step S3, the battery is left to stand for 3 to 6 hours after being assembled, and then the subsequent operation is performed.
Further, the electrical signal processing includes: one or more of constant current charge and discharge treatment, cyclic voltammetry treatment, or electrical pulse treatment.
Preferably, the constant current charge and discharge process includes: 1-5 mA cm -2 The current density of 1-5 mAh cm -2 The capacity charge and discharge of the reactor, and the treatment time is 6-20 hours;
preferably, the cyclic voltammetry treatment comprises: cycling for 8-30 times within the range of-1V at a scanning speed of 1-10 mV/s;
preferably, the electrical pulse processing includes: firstly, 8-40 mA.cm -2 Constant current charging with current density of 0.05-0.5 s, standing for 1-2 s, and charging with 8-40 mA cm -2 The current density constant current discharge is carried out for 0.05 to 0.5s, the operation is repeated, and the treatment time is 4 to 5 hours.
In the present invention, the method of processing the electrical signal and the selection of specific parameters may be set according to the kind of the negative electrode metal and the volume of the precursor solution. Generally, for a more active metal cathode, better effect can be achieved by using cyclic voltammetry and electric pulse treatment; the increase/decrease in the precursor solution volume requires an appropriate increase/decrease in the processing time.
Compared with the prior art, the invention has the beneficial effects that:
(1) According to the electropolymerization gel electrolyte battery and the preparation method thereof, provided by the invention, the gel monomer generates carbonyl free radical through an electrochemical method, a free radical initiator is not needed, and only a proper amount of cross-linking agent is needed to be added, so that the electropolymerization process can be used for in-situ preparation of the gel electrolyte, and the simplification of the formulation of the gel precursor solution is realized.
(2) According to the electropolymerized gel electrolyte battery and the preparation method thereof, the monomer molecules in the gel precursor contain N or O atoms capable of providing lone pair electrons or pi bonds containing a plurality of delocalized electrons, in the formation process of the electropolymerized gel electrolyte, the electrode surface and the precursor solution are subjected to charge transfer, the gel electrolyte is fully contacted with an interface, electrode metal ions accept more lone pair electrons or a plurality of delocalized electrons to form more coordination bonds for combining the two, so that the ionic conductivity is improved, the impedance of the electrode interface and the gel electrolyte is reduced, the bonding force between the electrode interface and the gel electrolyte is improved, and meanwhile, the structural stability in the charge and discharge processes of anode and cathode materials is improved, so that the electropolymerized gel electrolyte battery is widely applied to various irregular surfaces and bending scenes.
(3) According to the preparation method of the electropolymerized gel electrolyte battery, the gel stock solution immersed in the glass fiber diaphragm can form polymer network gel under the treatment of various electric signals, and the polymerization mode is various and flexible. The glass fiber diaphragm immersed in the gel precursor solution is used for assembling the battery and then is subjected to electric treatment to form a composite quasi-solid structure diaphragm, so that the preparation and assembly process of the gel electrolyte battery is simpler and more efficient, and the gel electrolyte battery is suitable for large-scale production and application.
Drawings
FIG. 1 is a cycle curve of a zinc symmetrical cell prepared in example 1 of the present invention;
FIG. 2 is a cycle curve of a zinc symmetrical cell prepared in example 2 of the present invention;
FIG. 3 is a cycle curve of a zinc symmetrical cell prepared in example 3 of the present invention;
FIG. 4 is a graph showing the cycle performance of the zinc full cell prepared in example 4 of the present invention;
FIG. 5 is a graph showing the cycle performance of the zinc full cell prepared in example 5 of the present invention;
FIG. 6 is a cycle curve of the zinc symmetrical cell manufactured in comparative example 1 of the present invention;
FIG. 7 is a cycle curve of the zinc symmetrical cell manufactured in comparative example 2 of the present invention;
FIG. 8 is a graph showing the cycle performance of the zinc full cell manufactured in comparative example 1 of the present invention;
FIG. 9 is a graph showing the cycle performance of the zinc full cell manufactured in comparative example 2 according to the present invention;
FIG. 10 shows the button cells of example 1, comparative example 1 and comparative example 2 according to the present invention at different cycles of 1mA cm -2 1mAh·cm -2 Impedance change contrast graph after constant current charge and discharge; wherein, (a) is the electropolymerized gel electrolyte cell of example 1; (b) An ultraviolet light polymerization gel electrolyte cell of comparative example 1; (c) a gel monomer solution battery of comparative example 2;
FIG. 11 shows the result of electrochemical polymerization of 1mA cm in the case of the electropolymerized gel electrolyte and the UV photopolymerized gel electrolyte -2 1mAh·cm -2 And after 60 cycles of constant current charge and discharge, comparing with the test result of the stripping force of the zinc sheet.
Detailed Description
The technical solutions of the present invention will be clearly and completely described in connection with the embodiments, and it is obvious that the described embodiments are only some embodiments of the present invention, not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
It should be noted that, without conflict, the embodiments of the present invention and features of the embodiments may be combined with each other.
The invention will be further illustrated with reference to specific examples, which are given by way of example, but not by way of limitation, of zinc ion batteries, as are lithium, sodium, aluminum and other metal ion batteries.
The cell types, polymerization modes, and electrical treatment methods of examples 1 to 5 and comparative examples 1 and 2 are shown in the following table 1.
TABLE 1
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Figure BDA0004082634210000071
Example 1
Step 1: preparing an aqueous hydrogel precursor solution comprising an ionic gel monomer and a crosslinking agent:
20.7g of 2-acrylamido-2-methylpropanesulfonic acid and 0.4g of N, N' -methylenebisacrylamide are dissolved in 50mL of deionized water, stirred at 60 ℃ for 30min, 5g of zinc oxide is slowly added into the solution, stirred and reacted for 30min, and excessive zinc oxide is centrifugally separated (6000 r/min) to obtain an electropolymerized ionic gel precursor aqueous solution containing zinc salt of 2-acrylamido-2-methylpropanesulfonic acid.
Step 2: the gel precursor solution infiltrates the glass fiber diaphragm, and the symmetrical battery is assembled:
selecting a glass fiber diaphragm with the thickness of 1+/-0.5 mm and the aperture of 2.7 mu m, cutting into a circular sheet with the diameter of 1.6cm, dropwise adding 45 mu L of ionic gel precursor aqueous solution on the front side and the back side of the circular sheet, placing the wetted diaphragm in a dark and low-temperature environment for 1 hour, transferring the circular sheet into a vacuum box, vacuumizing to 0.01MPa, maintaining the pressure for 20 minutes, introducing nitrogen, and packaging into a CR2032 button cell with a zinc sheet (with the thickness of 0.1 mm) as a negative electrode sheet, thereby assembling the paired cells.
Step 3: preparation of an electropolymerized gel electrolyte cell by electrical treatment:
standing for 5 hours after the zinc symmetrical battery is assembled, and setting 1mA cm -2 1mAh·cm -2 And (3) constant-current charge and discharge treatment conditions, and treating for 8 hours to obtain the electropolymerized gel electrolyte battery.
Example 2
Step 1: preparing an aqueous hydrogel precursor solution comprising an ionic gel monomer and a crosslinking agent:
20.7g of 2-acrylamido-2-methylpropanesulfonic acid and 0.4g of N, N' -methylenebisacrylamide are dissolved in 50mL of deionized water, stirred at 60 ℃ for 30min, 5g of zinc oxide is slowly added into the solution, stirred and reacted for 30min, and excessive zinc oxide is centrifugally separated (6000 r/min) to obtain an electropolymerized ionic gel precursor aqueous solution containing zinc salt of 2-acrylamido-2-methylpropanesulfonic acid.
Step 2: the gel precursor solution infiltrates the glass fiber diaphragm, and the symmetrical battery is assembled:
selecting a glass fiber diaphragm with the thickness of 1+/-0.5 mm and the aperture of 2.7 mu m, cutting into a circular sheet with the diameter of 1.6cm, dropwise adding 45 mu L of ionic gel precursor aqueous solution on the front side and the back side of the circular sheet, placing the wetted diaphragm in a dark and low-temperature environment for 1 hour, transferring the circular sheet into a vacuum box, vacuumizing to 0.01MPa, maintaining the pressure for 20 minutes, introducing nitrogen, and packaging into a CR2032 button cell with a zinc sheet (with the thickness of 0.1 mm) as a negative electrode sheet, thereby assembling the paired cells.
Step 3: preparation of an electropolymerized gel electrolyte cell by electrical treatment:
and standing for 5 hours after the zinc symmetrical battery is assembled, setting a scanning speed of 1mV/s and a cyclic voltammetry treatment condition within a range of-1V, and circulating for 18 times to obtain the electropolymerized gel electrolyte battery.
Example 3
Step 1: preparing an aqueous hydrogel precursor solution comprising an ionic gel monomer and a crosslinking agent:
20.7g of 2-acrylamido-2-methylpropanesulfonic acid and 0.4g of N, N' -methylenebisacrylamide are dissolved in 50mL of deionized water, stirred at 60 ℃ for 30min, 5g of zinc oxide is slowly added into the solution, stirred and reacted for 30min, and excessive zinc oxide is centrifugally separated (6000 r/min) to obtain an electropolymerized ionic gel precursor aqueous solution containing zinc salt of 2-acrylamido-2-methylpropanesulfonic acid.
Step 2: the gel precursor solution infiltrates the glass fiber diaphragm, and the symmetrical battery is assembled:
selecting a glass fiber diaphragm with the thickness of 1+/-0.5 mm and the aperture of 2.7 mu m, cutting into a circular sheet with the diameter of 1.6cm, dropwise adding 45 mu L of ionic gel precursor aqueous solution on the front side and the back side of the circular sheet, placing the wetted diaphragm in a dark and low-temperature environment for 1 hour, transferring the circular sheet into a vacuum box, vacuumizing to 0.01MPa, maintaining the pressure for 20 minutes, introducing nitrogen, and packaging into a CR2032 button cell with a zinc sheet (with the thickness of 0.1 mm) as a negative electrode sheet, thereby assembling the paired cells.
Step 3: preparation of an electropolymerized gel electrolyte cell by electrical treatment:
standing for 5 hours after the zinc symmetrical battery is assembled, and setting 10mA cm -2 Constant current charging, time interval of 0.1s, standing for 1s, 10mA.cm -2 Constant-current discharge and electric pulse treatment conditions with time interval of 0.1s for 5 hours to obtain electropolymerized gelAn electrolyte cell.
Example 4
Step 1: preparing an aqueous hydrogel precursor solution comprising an ionic gel monomer and a crosslinking agent:
20.7g of 2-acrylamido-2-methylpropanesulfonic acid and 0.4g of N, N' -methylenebisacrylamide are dissolved in 50mL of deionized water, stirred at 60 ℃ for 30min, 5g of zinc oxide is slowly added into the solution, stirred and reacted for 30min, and excessive zinc oxide is centrifugally separated (6000 r/min) to obtain an electropolymerized ionic gel precursor aqueous solution containing zinc salt of 2-acrylamido-2-methylpropanesulfonic acid.
Step 2: the gel precursor solution infiltrates the glass fiber diaphragm, and the full cell is assembled:
selecting a glass fiber diaphragm with the thickness of 1+/-0.5 mm and the aperture of 2.7 mu m, cutting into a circular sheet with the diameter of 1.6cm, dropwise adding 45 mu L of ionic gel precursor aqueous solution into the front and back sides of the circular sheet, placing the wetted diaphragm in a dark and low-temperature environment for 1 hour, transferring the circular sheet into a vacuum box, vacuumizing to 0.01MPa, maintaining the pressure for 20 minutes, introducing nitrogen, loading the circular sheet into a CR2032 button battery with a zinc sheet (with the thickness of 0.1 mm) as a negative electrode sheet and a titanium foil (with the thickness of 20 mu m) adhered with a positive electrode coating film as a positive electrode sheet, and assembling the circular sheet into a full battery.
The prepared positive electrode film coated on the titanium foil has the thickness of 50+/-5 mu m, is dried for 12 hours at 80 ℃ and is sheared into a wafer with the diameter of 12mm, so that the positive electrode plate is obtained. The components of the positive electrode coating film comprise 80wt.% of manganese dioxide active material, 10wt.% of acetylene black conductive agent and 10wt.% of polyvinylidene fluoride binder, and the loading of the positive electrode plate active material is 0.64-0.72 mg.
Step 3: preparation of an electropolymerized gel electrolyte cell by electrical treatment:
and standing for 5 hours after the zinc full cell is assembled, setting a scanning speed of 1mV/s and a cyclic voltammetry treatment condition within a range of 0-2V, and circulating for 18 times to obtain the electropolymerized gel electrolyte cell.
Example 5
Step 1: preparing an aqueous hydrogel precursor solution comprising an ionic gel monomer and a crosslinking agent:
20.7g of 2-acrylamido-2-methylpropanesulfonic acid and 0.4g of N, N' -methylenebisacrylamide are dissolved in 50mL of deionized water, stirred at 60 ℃ for 30min, 5g of zinc oxide is slowly added into the solution, stirred and reacted for 30min, and excessive zinc oxide is centrifugally separated (6000 r/min) to obtain an electropolymerized ionic gel precursor aqueous solution containing zinc salt of 2-acrylamido-2-methylpropanesulfonic acid.
Step 2: the gel precursor solution infiltrates the glass fiber diaphragm, and the full cell is assembled:
selecting a glass fiber diaphragm with the thickness of 1+/-0.5 mm and the aperture of 2.7 mu m, cutting into a circular sheet with the diameter of 1.6cm, dropwise adding 45 mu L of ionic gel precursor aqueous solution into the front and back sides of the circular sheet, placing the wetted diaphragm in a dark and low-temperature environment for 1 hour, transferring the circular sheet into a vacuum box, vacuumizing to 0.01MPa, maintaining the pressure for 20 minutes, introducing nitrogen, loading the circular sheet into a CR2032 button battery with a zinc sheet (with the thickness of 0.1 mm) as a negative electrode sheet and a titanium foil (with the thickness of 20 mu m) adhered with a positive electrode coating film as a positive electrode sheet, and assembling the circular sheet into a full battery.
The prepared positive electrode film coated on the titanium foil has the thickness of 50+/-5 mu m, is dried for 12 hours at 80 ℃ and is sheared into a wafer with the diameter of 12mm, so that the positive electrode plate is obtained. The components of the positive electrode coating film comprise 80wt.% of manganese dioxide active material, 10wt.% of acetylene black conductive agent and 10wt.% of polyvinylidene fluoride binder, and the loading of the positive electrode plate active material is 0.64-0.72 mg.
Step 3: preparation of an electropolymerized gel electrolyte cell by electrical treatment:
standing for 5 hours after the zinc full cell is assembled, and setting 1mA cm -2 Constant current discharge to 1.8V, 1 mA.cm -2 And (3) constant-current charging to 0.2V constant-current charging and discharging treatment conditions, and circulating for 12 times to obtain the electropolymerized gel electrolyte battery.
Comparative example 1
Step 1: preparing an ultraviolet polymerization gel electrolyte precursor aqueous solution:
20.7g of 2-acrylamido-2-methylpropanesulfonic acid, 0.4g of N, N' -methylenebisacrylamide and 0.4g of 2-hydroxy-2-methyl-1-phenyl ketone are dissolved in 50mL of deionized water, stirred at 60 ℃ for 30min, then 5g of zinc oxide is slowly added into the solution, stirred and reacted for 30min, and excessive zinc oxide is centrifugally separated (6000 r/min) to obtain an ultraviolet light polymerization ionic gel precursor aqueous solution containing zinc salt of 2-acrylamido-2-methylpropanesulfonic acid.
Step 2: and assembling the symmetrical battery and the full battery after photopolymerization of the ultraviolet light polymerization ionic gel precursor aqueous solution in the glass fiber diaphragm:
selecting a glass fiber diaphragm with the thickness of 1+/-0.5 mm and the aperture of 2.7 mu m, cutting into a circular sheet with the diameter of 1.6cm, dropwise adding 45 mu L of ultraviolet light polymerization ionic gel precursor aqueous solution on the front side and the back side of the circular sheet respectively, placing the wetted diaphragm in a dark and low-temperature environment for 1 hour, transferring into a vacuum box, vacuumizing to 0.01MPa, maintaining the pressure for 20 minutes, introducing nitrogen, transferring the wetted diaphragm into a glass container, introducing nitrogen, sealing the container after the atmosphere of nitrogen is adopted in the glass container, irradiating for 8 hours under an ultraviolet lamp with 365nm to obtain a photopolymerization hydrogel electrolyte diaphragm of composite glass fiber paper, and putting the photopolymerization hydrogel electrolyte diaphragm into a CR2032 button cell with a zinc sheet (with the thickness of 0.1 mm) serving as a negative electrode sheet to assemble the symmetrical cell.
In addition, a full cell was assembled by incorporating a CR2032 button cell having a zinc plate (thickness of 0.1 mm) as a negative electrode sheet and a titanium foil (thickness of 20 μm) to which a positive electrode coating film was adhered.
The prepared positive electrode film coated on the titanium foil has the thickness of 50+/-5 mu m, is dried for 12 hours at 80 ℃ and is sheared into a wafer with the diameter of 12mm, so that the positive electrode plate is obtained. The components of the positive electrode coating film comprise 80wt.% of manganese dioxide active material, 10wt.% of acetylene black conductive agent and 10wt.% of polyvinylidene fluoride binder, and the loading of the positive electrode plate active material is 0.64-0.72 mg.
Comparative example 2
Step 1: preparation of monomer solution electrolyte:
20.7g of 2-acrylamido-2-methylpropanesulfonic acid is dissolved in 50mL of deionized water, stirred at 60 ℃ for 30min, then 5g of zinc oxide is slowly added into the solution, the stirring reaction is carried out for 30min, and excessive zinc oxide is centrifugally separated (6000 r/min) to obtain a solution electrolyte of which the monomer is zinc salt of 2-acrylamido-2-methylpropanesulfonic acid.
Step 2: and (3) after the monomer solution electrolyte is immersed in the glass fiber diaphragm, assembling the symmetrical battery and the full battery:
selecting a glass fiber diaphragm with the thickness of 1+/-0.5 mm and the aperture of 2.7 mu m, cutting into a circular sheet with the diameter of 1.6cm, dropwise adding 45 mu L of monomer solution on the front side and the back side of the circular sheet respectively, placing the wetted diaphragm in a dark and low-temperature environment for 1 hour, transferring into a vacuum box, vacuumizing to 0.01MPa, maintaining the pressure for 20 minutes, introducing nitrogen, and packaging the circular sheet into a CR2032 button battery with a zinc sheet (with the thickness of 0.1 mm) as a negative pole piece, thereby assembling the symmetrical battery.
In addition, a full cell was assembled by incorporating a CR2032 button cell having a zinc plate (thickness of 0.1 mm) as a negative electrode sheet and a titanium foil (thickness of 20 μm) to which a positive electrode coating film was adhered.
The prepared positive electrode film coated on the titanium foil has the thickness of 50+/-5 mu m, is dried for 12 hours at 80 ℃ and is sheared into a wafer with the diameter of 12mm, so that the positive electrode plate is obtained. The components of the positive electrode coating film comprise 80wt.% of manganese dioxide active material, 10wt.% of acetylene black conductive agent and 10wt.% of polyvinylidene fluoride binder, and the loading of the positive electrode plate active material is 0.64-0.72 mg.
Performance testing
First cycle and capacity performance test
The zinc symmetrical cells prepared in examples 1 to 3 were subjected to a treatment of 1mA cm -2 Constant current circulation charge and discharge test of current density, and the set charge and discharge capacity is 1mAh cm -2 The method comprises the steps of carrying out a first treatment on the surface of the The batteries prepared in examples 4 and 5 were subjected to constant current charge and discharge test, and the constant current density was set to 0.1 A.g -1 。
The zinc symmetrical cells prepared in comparative examples 1 and 2 were subjected to a process of 1mA cm -2 Constant current cycle charge and discharge test of current density (set charge and discharge capacity of 1mAh cm) -2 ) The zinc full cells prepared in comparative examples 1 and 2 were subjected to constant current charge and discharge test (constant current density of 0.1 A.g was set -1 )。
The test results are shown in FIGS. 1-10.
From fig. 1 to 3, 6 and 7, the symmetrical cells of examples 1 to 3 each have a cycle life of more than 2000 hours as compared with the results of the symmetrical cell test of comparative examples 1 and 2, and the symmetrical cells of comparative examples 1 and 2 are mainly short-circuited to interrupt the cell cycle due to dendrite growth, which shows that the electropolymerized gel electrolyte provided by the present invention can uniformly generate the dissolution/deposition process of zinc ions, which can effectively solve the problem of zinc dendrite growth.
As can be seen from fig. 4, 5, 8 and 9, the electropolymerized gel electrolyte provides the aqueous zinc ion full cell with relatively better cycle performance as compared with the full cell of comparative examples 1 and 2, and has significantly higher capacity retention than the uv polymerized gel electrolyte and the non-gel monomer solution electrolyte full cell, which indicates that the electropolymerized gel electrolyte also provides a degree of protection for the metal ion battery anode.
Further, FIGS. 10 (a) (b) (c) are respectively schematic illustrations of symmetrical cells of example 1, comparative example 1 and comparative example 2 at 1mA cm -2 1mAh·cm -2 The impedance test immediately carried out after different cycle periods (2, 5, 10, 30 and 60 periods) of constant current charge and discharge shows that the electropolymerized gel electrolyte battery has smaller capacitance arc radius after each cycle period, and shows that the electropolymerized gel electrolyte has lower charge transfer resistance at an interface, particularly after 5 cycles, the electropolymerized gel electrolyte improves the problems of zinc negative electrodes such as corrosion, passivation and the like, ensures that the surface of the electrode maintains a better activation state for a long time, and plays a role in stabilizing the surface of the zinc negative electrode.
(II) Peel test
Cutting the glass fiber membrane into 70mm long and 40mm wide, dropwise adding 630 mu L of electropolymerized ionic gel precursor aqueous solution into the front and back sides of the glass fiber membrane, taking two zinc sheets with the length of 40-60 mm and the width of 20-30 mm, polishing to 2000 meshes, and clamping the zinc sheets at the middle positions of the two sides of the membrane to prepare the zinc sheet/glass fiber membrane/zinc sheet three-layer structure. The three-layer structure was clamped with two 100X 100mm glass plates leaving 10mm long for external power. Setting 1mA cm -2 1mAh·cm -2 The constant current charge and discharge treatment conditions of (1) and (60) hours later, the glass plate is removed, and two zinc sheets are arrangedThe remaining portions were fixed to two clamps of a peel force tester, respectively, and then peel test was performed at a speed of 1mm/min under a load of 10N until the three-layer structure was peeled off. In addition, 630. Mu.L of ultraviolet light polymerization ionic gel precursor aqueous solution is respectively dripped on the front side and the back side of the glass fiber diaphragm with the same size, the wetted diaphragm is subjected to photopolymerization by the method described in comparative example 1, two zinc sheets with the length of 40-60 mm and the width of 20-30 mm are polished to the middle position of two sides of the diaphragm, and the zinc sheet/glass fiber diaphragm/zinc sheet three-layer structure is prepared, and is clamped by two 100X 100mm glass plates, and the three-layer structure is subjected to peeling test after the same constant current charge and discharge treatment. The test results are shown in fig. 11.
As can be seen from FIG. 11, the peeling test showed that after the same conditions of the electric treatment (1 mA cm -2 1mAh·cm -2 Constant current charge and discharge 60 cycles), compared with the ultraviolet light polyelectrolyte and the zinc sheet electrode, the electropolymerized gel electrolyte prepared by the electrochemical polymerization method provided by the invention has stronger bonding force, and the bonding force with the zinc sheet electrode is about 2 times of that of the ultraviolet light polyelectrolyte, which indicates that the electropolymerized gel electrolyte battery can be more suitable for being applied to various irregular surfaces and bending scenes.
In conclusion, the electro-gel electrolyte battery provided by the invention has excellent cycle performance and capacity retention rate, can stabilize the surface of a zinc anode, has stronger binding force between the gel electrolyte and an electrode plate, has strong stripping resistance, and can be more suitable for being applied to various irregular surfaces and bending scenes. Importantly, the raw material components of the preparation method are simplified and are easy to obtain, the battery assembly steps are simple, the preparation method is suitable for large-scale production, and the preparation method has wide popularization and application prospects.
The foregoing is merely illustrative of the preferred embodiments of the present invention and is not intended to limit the embodiments and scope of the present invention, and it should be appreciated by those skilled in the art that equivalent substitutions and obvious variations may be made using the teachings of the present invention, which are intended to be included within the scope of the present invention.

Claims (10)

1. An electropolymerized gel electrolyte cell comprising a negative electrode, a positive electrode, and a gel electrolyte; it is characterized in that the method comprises the steps of,
the negative electrode is a metal electrode;
the gel electrolyte is prepared by in-situ polymerization of gel precursor solution infiltrated into a diaphragm in a battery through electric signal treatment;
the gel precursor solution includes an anionic polymer monomer and a crosslinking agent.
2. A method for preparing an electropolymerized gel electrolyte cell, comprising the steps of:
s1, preparing gel precursor solution containing anionic polymer monomers and a cross-linking agent;
s2, infiltrating the gel precursor solution into a glass fiber diaphragm to obtain an infiltrated diaphragm;
s3, assembling the infiltrated diaphragm, the anode and the metal cathode into a battery, and carrying out in-situ polymerization on the gel precursor solution in the battery to form a gel electrolyte under the treatment of an electric signal to obtain the electropolymerized gel electrolyte battery.
3. The method according to claim 2, wherein in the step S1, the gel precursor solution is prepared by mixing 20 to 40wt.% of the anionic polymer monomer, 0.4 to 1.0wt.% of the crosslinking agent, and the balance being water or an organic solvent.
4. A process according to claim 3, wherein,
the anionic polymer monomer is selected from one or a combination of more of 2-acrylamide-2-methylpropanesulfonic acid sodium salt, 2-acrylamide-2-methylpropanesulfonic acid zinc salt, acrylic acid sodium salt, methacrylic acid sodium salt, ethylene sulfonic acid sodium salt, styrene sulfonic acid sodium salt and p-vinylbenzene sulfonic acid sodium salt;
the cross-linking agent is selected from one or a combination of more of N, N' -methylene bisacrylamide and derivatives thereof or ethylene glycol dimethacrylate and derivatives thereof.
5. The method according to claim 2, wherein in the step S2, the glass fiber membrane has a thickness of 1 to 1.2mm and a pore diameter of 2.5 to 3.0 μm; the volume of the gel precursor solution accounts for 40-50% of the volume of the glass fiber diaphragm.
6. The method according to claim 2, wherein in the step S3, the metal of the metal anode is selected from one of zinc, lithium, sodium, and aluminum.
7. The method of manufacturing according to claim 2, wherein the electrical signal processing includes: one or more of constant current charge and discharge treatment, cyclic voltammetry treatment, or electrical pulse treatment.
8. The method according to claim 7, wherein the constant current charge and discharge treatment comprises: 1-5 mA cm -2 The current density of 1-5 mAh cm -2 The capacity charge and discharge of the reactor is 6 to 20 hours.
9. The method of claim 7, wherein the cyclic voltammetry treatment comprises: cycling for 8-30 times at a scanning speed of 1-10 mV/s and a range of-1V.
10. The method of claim 7, wherein the electrical pulse treatment comprises: firstly, 8-40 mA.cm -2 Constant current charging with current density of 0.05-0.5 s, standing for 1-2 s, and charging with 8-40 mA cm -2 The current density constant current discharge is carried out for 0.05 to 0.5s, the operation is repeated, and the treatment time is 4 to 5 hours.
CN202310127663.9A 2023-02-14 2023-02-14 Electropolymerized gel electrolyte battery and preparation method thereof Pending CN116093426A (en)

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