CN114725535A - Gel electrolyte capable of effectively inhibiting zinc dendrites and preparation method and application thereof - Google Patents

Gel electrolyte capable of effectively inhibiting zinc dendrites and preparation method and application thereof Download PDF

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CN114725535A
CN114725535A CN202210342547.4A CN202210342547A CN114725535A CN 114725535 A CN114725535 A CN 114725535A CN 202210342547 A CN202210342547 A CN 202210342547A CN 114725535 A CN114725535 A CN 114725535A
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electrolyte
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zinc
gel electrolyte
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CN114725535B (en
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程菲
刘泽飞
李焕荣
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Hebei University of Technology
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    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
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    • C08F220/06—Acrylic acid; Methacrylic acid; Metal salts or ammonium salts thereof
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Abstract

The invention belongs to the field of energy storage materials, and relates to a water system zinc ion battery; in particular to a gel electrolyte for effectively inhibiting zinc dendrites, a preparation method and application thereof. Polymerization by incorporating nanosized hectorites into polymer hydrogelsThe gel electrolyte is synthesized, and the mechanical strength of the composite gel electrolyte can be effectively improved by utilizing the characteristic that the hectorite can attract long polymer chains; the uniform deposition of zinc ions is guided by utilizing the charge characteristic of the hectorite in a water system. Meanwhile, the invention also provides a preparation method of the gel electrolyte for effectively inhibiting the zinc dendrite, the method is simple in process and suitable for industrialization, and the prepared gel electrolyte can effectively inhibit the zinc dendrite and side reaction; the gel electrolyte and MnO2The flexible quasi-solid ZIB composed of @8% rGO anode and electrodeposited zinc @ carbon cloth anode can stably supply power for an electronic display in a severe environment of shearing and bending.

Description

Gel electrolyte capable of effectively inhibiting zinc dendrites and preparation method and application thereof
Technical Field
The invention belongs to the field of energy storage materials, and relates to a water system zinc ion battery; in particular to a gel electrolyte for effectively inhibiting zinc dendrite and a preparation method and application thereof.
Background
The development of flexible wearable electronics has led to extensive research into batteries with special characteristics of flexibility, safety, and high performance. Compared with a rigid battery with a liquid electrolyte, the solid-state battery is more beneficial to design and processing with high flexibility, high wear resistance and leakage-proof performance. Over the past few decades, Lithium Ion Batteries (LIBs) have dominated energy storage devices by virtue of high energy density. However, it is very challenging to apply it to flexible energy storage devices. In recent years, aqueous Zinc Ion Batteries (ZIBs) have emerged as a promising energy storage battery. The water system zinc ion battery has low cost, abundant required material resources and environmental friendliness, and is expected to replace LIBs (lithium ion batteries) for large-scale application. The quasi-solid battery consists of four components, namely a positive electrode, a negative electrode (zinc metal), a quasi-solid electrolyte and a current collector. The hydrogel electrolyte is sandwiched between the positive electrode and the negative electrode as a quasi-solid electrolyte, and has a significant effect on the performance of the entire battery.
Currently, various gel electrolytes have been studied and applied to ZIBs. However, because of the lower ionic conductivity of gel electrolytes, the performance of quasi-solid state zinc ion batteries is still not comparable to batteries using liquid electrolytes, especially the high rate performance. However, whether the gel electrolyte can effectively inhibit the side reaction and the zinc dendrite in the reaction process, and how to make the gel electrolyte have good flexibility, mechanical strength and higher ionic conductivity is a main problem existing in the water system zinc ion battery at present. Chen et al used cotton, tetraethyl orthosilicate (crosslinker) and glycerol (antifreeze) to design a gel electrolyte with high ionic conductivity and high tensile strength that can significantly suppress zinc dendrites and side reactions; but its mechanical strength is not strong enough. Xu et al reported a Cellulose Nanofiber (CNF) -Polyacrylamide (PAM) -based hydrogel electrolyte with high tensile properties and strong mechanical stability; but is not strong against side reactions and zinc dendrite inhibition. Therefore, the design and synthesis of polymer electrolytes with high ionic conductivity, mechanical and electrochemical properties are very important for ZIBs.
Disclosure of Invention
Aiming at the problems that the cycling stability of a water-based zinc ion battery is affected by the occurrence of side reactions and serious zinc dendrites in the cycling process of the water-based zinc ion battery, the invention provides a gel electrolyte for effectively inhibiting the zinc dendrites, and the mechanical strength of the composite gel electrolyte can be effectively improved by introducing nano-sized hectorite into polymer hydrogel to polymerize into the gel electrolyte and utilizing the characteristic that the hectorite can attract long polymer chains; the uniform deposition of zinc ions is guided by utilizing the charged characteristic of the hectorite in a water system.
Meanwhile, the invention also provides a preparation method of the gel electrolyte for effectively inhibiting the zinc dendrites, the method is simple in process and suitable for industrialization, and the prepared gel electrolyte can effectively inhibit the zinc dendrites and side reactions; the gel electrolyte and MnO2The flexible quasi-solid ZIB composed of @8% rGO anode and electrodeposited zinc @ carbon cloth anode can stably supply power for an electronic display in a severe environment of shearing and bending.
The technical scheme of the invention is as follows:
a gel electrolyte effective in inhibiting zinc dendrites, the starting materials comprising: electrolyte solutions, polymer hydrogels, hectorites; specifically, the hectorite is added in the formation process of the polymer hydrogel after being uniformly mixed in the electrolyte solution.
Preferably, the polymer hydrogel is: one of polyacrylic acid, polyethylene glycol, polyvinyl alcohol and polymethacrylic acid hydrogel; the electrolyte solution is as follows: zinc sulfate, distilled water and manganese sulfate.
Preferably, the raw materials of the polymer hydrogel comprise a polymer monomer, an initiator and a cross-linking agent;
the polymer monomers are: acrylic acid, methacrylic acid or acrylamide, wherein the initiator is ammonium persulfate or potassium persulfate, and the cross-linking agent is N, N-methylene-bisacrylamide;
the polymer monomers are: hexapolyethylene glycol and glycerol, wherein the initiator is dimethylaminopyridine, and the cross-linking agent is divinyl sulfone;
the polymer monomers are: polyvinyl alcohol, initiator NaOH and cross-linking agent epichlorohydrin.
Preferably, the adding amount of the hectorite is 0.1-40% of the mass of the electrolyte solution.
Preferably, the mass ratio of the hectorite to the polymer monomer is: 40-800:1200-1960.
The preparation method of the gel electrolyte for effectively inhibiting the zinc dendrites comprises the following steps:
(1) preparation of electrolyte solution: zinc sulfate, distilled water and manganese sulfate are mixed to prepare the zinc sulfate-manganese sulfate water-based paint;
(2) preparation of a polymerization precursor mixture: adding hectorite into a part of electrolyte solution, uniformly dispersing, adding a polymer monomer, and continuously stirring to obtain a solution 1; meanwhile, adding a cross-linking agent into a part of electrolyte solution, and uniformly dispersing to obtain a solution 2; adding an initiator into the rest electrolyte solution, and uniformly dispersing to obtain a solution 3; adding the solution 2 and the solution 3 into the solution 1 to form a uniform polymerization precursor mixed solution;
(3) polymerization of the composite gel electrolyte: and injecting the polymerization precursor mixed solution into a mold, wrapping the mixture with a metal aluminum foil in the dark, and polymerizing for 1-3 h at the temperature of 60-80 ℃ to obtain the polymer-Lap composite hydrogel electrolyte.
Preferably, the electrolyte solution of the step (1) is 2 mol/L ZnSO4And 0.2 mol/L MnSO4The mixed aqueous solution of (1).
The gel electrolyte for effectively inhibiting the zinc dendrite is applied to an aqueous zinc ion battery.
The invention has the beneficial effects that:
1. proper hectorite doping can obtain the composite gel electrolyte with high mechanical property and high ionic conductivity.
Prior studies have generally inhibited the zinc dendrite problem by either enhancing the strength of the gel electrolyte or directing uniform deposition of zinc ions. The invention utilizes the special performance of the hectorite to enhance the strength of the PAM hydrogel and simultaneously lead the PAM hydrogel to obtain the function of guiding zinc ions to be uniformly deposited. According to the invention, the hectorite is used as an additive, and the characteristic that the hectorite can attract long polymer chains is utilized, so that the mechanical strength of the composite gel electrolyte can be effectively improved; in addition, the hectorite can be ionized into a lamellar structure with a negative center and a weak positive edge in a water system, and the lamellar structure is uniformly dispersed in the composite electrolyte and can guide the uniform deposition of zinc ions. The composite hydrogel obtained by the preparation not only showed a tensile strength of 45kPa and an elongation at break of 606%, but also had a length of 20.3 mS cm-1High ion conductivity.
2. The prepared water-based zinc ion battery has large reversible capacity and 2A g-1After 2000 times of circulation under high current density, 97 mAh g is still kept-1Specific discharge capacity of
It was assembled in a Zn// Zn symmetrical cell at 0.5 mA cm-2At a current density of (2), the Zn// PAM-Lap// Zn symmetric cell showed consistent low voltage polarization of less than 60 mV over 2000 hours. By performing SEM analysis on the zinc sheet after the circulation of the Zn// Zn symmetric battery, the composite hydrogel can effectively inhibit zinc dendrites. It can be seen that when the composite hydrogel of the present application is applied to MnO2291 mAh g can be shown when the @8 percent rGO is used as a zinc ion battery of a cathode-1Reversible capacity of 2A g-1ZIB using PAM-Lap-3 as electrolyte still maintains 97 mAh g after 2000 cycles under high current density-1Specific discharge capacity of (2).
3. Can stably supply power for the electronic display under the severe environment of shearing and bending
By MnO2The flexible quasi-solid ZIB composed of @8% rGO positive electrode, PAM-Lap electrolyte and electrodeposited zinc @ carbon cloth anode can stably supply power for an electronic display in a severe environment of shearing and bending. This provides a theoretical basis for the development of flexible zinc ion batteries.
Drawings
FIG. 1 is a graph showing tensile properties of a PAM-Lap-1 composite hydrogel electrolyte in comparative example 1;
FIG. 2 is an EIS of the PAM-Lap-1 composite hydrogel electrolyte in comparative example 1;
FIG. 3 is a voltage-time curve of a Zn// Zn symmetric cell corresponding to the PAM-Lap-1 gel electrolyte in comparative example 1;
FIG. 4 is a scanning electron micrograph of the zinc plate after 800 cycles of the Zn// PAM-Lap-1// Zn symmetric cell of comparative example 1;
FIG. 5 is a graph showing tensile properties of the PAM-Lap-2 composite hydrogel electrolyte of example 1;
FIG. 6 is an EIS of the PAM-Lap-2 composite hydrogel electrolyte of example 1;
FIG. 7 is a voltage-time curve of a Zn// Zn symmetric cell corresponding to the PAM-Lap-2 gel electrolyte of example 1;
FIG. 8 is an optical photograph of a twist demonstration of the PAM-Lap-3 composite hydrogel electrolyte in example 2;
FIG. 9 is an optical picture of a tensile demonstration of the PAM-Lap-3 composite hydrogel electrolyte in example 2;
FIG. 10 is an optical picture demonstrating the self-healing performance of the PAM-Lap-3 composite hydrogel electrolyte in example 2;
FIG. 11 is a scanning electron micrograph of the PAM-Lap-3 composite hydrogel electrolyte in example 2 after drying;
FIG. 12 is a graph showing tensile properties of the PAM-Lap-3 composite hydrogel electrolyte of example 2;
FIG. 13 is an EIS of the PAM-Lap-3 composite hydrogel electrolyte of example 2;
FIG. 14 is a chronoamperometric curve (inset is EIS before and after polarization) of Zn// PAM-Lap-3// Zn cell in example 2.
FIG. 15 is a voltage-time curve of a Zn// Zn symmetric cell corresponding to the PAM-Lap-3 gel electrolyte of example 2;
FIG. 16 is a scanning electron micrograph of the zinc plate after 800 cycles of the Zn// PAM-Lap-3// Zn symmetric cell of example 2;
fig. 17 is a rate performance curve of the full cell in example 2;
fig. 18 is a long cycle performance curve of the full cell in example 2;
FIG. 19 is an optical image of the flexible battery in example 2 after being subjected to damage by PAM-Lap-3;
FIG. 20 is an optical image of PAM-Lap-3 of example 2 when bent after being applied to a flexible battery;
FIG. 21 is a graph showing tensile properties of the PAM-Lap-4 composite hydrogel electrolyte of example 3;
FIG. 22 is an EIS of the PAM-Lap-4 composite hydrogel electrolyte of example 3;
FIG. 23 is a voltage-time curve of a Zn// Zn symmetric cell corresponding to the PAM-Lap-4 gel electrolyte in example 3.
Detailed Description
Comparative example 1
A preparation method of a gel electrolyte for effectively inhibiting zinc dendrites comprises the following steps:
(1) 2 g of acrylamide was added to 8 ml of the electrolyte solution, and stirred for a certain period of time to be uniformly dispersed. Simultaneously, 2.5 mg of N, N-dimethyl bisacrylamide is added into 1 ml of electrolyte solution, and the electrolyte solution is subjected to ultrasonic treatment to be uniformly dispersed; 15 mg of ammonium persulfate is also added into 1 ml of electrolyte solution, and ultrasonic dispersion is carried out to be uniform. They were added to the acrylamide monomer solution and stirred for 30 minutes to form a uniform polymerization precursor mixture.
(2) And then injecting the precursor mixed solution into a mold with a designed thickness, wrapping the mold with a metal aluminum foil in the dark, and polymerizing for 1-2 hours at the temperature of 60-80 ℃ to obtain the PAM-Lap-1 hydrogel electrolyte.
The zinc/iron complex is used as an electrolyte and applied to a ss/ss symmetric battery to calculate the ionic conductivity, and is applied to a Zn/Zn symmetric battery to represent the inhibition effect on zinc dendrites. (ss is a stainless steel sheet)
FIG. 1 is a stress-strain curve of a PAM-Lap-1 composite hydrogel electrolyte, PAM-Lap-1 having a tensile strength of 36 kPa and an elongation at break of 527%
FIG. 2 is an EIS curve of the PAM-Lap-1 composite hydrogel electrolyte, and the ionic conductivity of the PAM-Lap-1 composite hydrogel electrolyte calculated by a fitting circuit is 8.7 mS cm-1。
FIG. 3 shows the voltage of a Zn// Zn symmetrical cell corresponding to PAM-Lap-1Time curve at 0.5 mA cm-2At current densities of (a), the Zn// PAM-Lap-1// Zn symmetric cell showed a potential rise after 1200 hours, indicating that unstable zinc plating/dissolution occurred.
FIG. 4 is a scanning electron microscope image of a zinc sheet obtained after the PAM-Lap-1 hydrogel electrolyte is applied to a Zn// Zn symmetric battery and circulates for 800 hours, the surface of the zinc sheet is damaged and has less serious dendrite protrusions, and the PAM composite hydrogel electrolyte inhibits the growth of zinc dendrite to a certain extent.
Example 1
A preparation method of a gel electrolyte for effectively inhibiting zinc dendrites comprises the following steps:
(1) adding zinc sulfate and manganese sulfate into distilled water, dissolving by ultrasonic wave, and fixing volume in a volumetric flask to obtain 2 mol/L ZnSO4And 0.2 mol/L MnSO4The mixed aqueous solution of (1).
(2) Adding 40 mg of hectorite into 8 ml of electrolyte solution, stirring for a certain time, uniformly dispersing, adding 1960 mg of acrylamide monomer, and continuously stirring for 20-30 minutes. Simultaneously, 2.5 mg of N, N-dimethyl bisacrylamide is added into 1 ml of electrolyte solution, and the electrolyte solution is subjected to ultrasonic treatment to be uniformly dispersed; 15 mg of ammonium persulfate is also added into 1 ml of electrolyte solution, and ultrasonic dispersion is carried out to be uniform. They were added to a solution of hectorite and acrylamide monomers and stirred for 30 minutes to form a homogeneous polymerization precursor mixture.
(3) And then injecting the precursor mixed solution into a mold with a designed thickness, wrapping the mold with a metal aluminum foil in the dark, and polymerizing for 1-2 hours at the temperature of 60-80 ℃ to obtain the PAM-Lap-2 composite hydrogel electrolyte.
The zinc/iron complex is used as an electrolyte and applied to a ss/ss symmetric battery to calculate the ionic conductivity, and is applied to a Zn/Zn symmetric battery to represent the inhibition effect on zinc dendrites.
FIG. 5 is a stress-strain curve of a PAM-Lap-2 composite hydrogel electrolyte, PAM-Lap-2 having a tensile strength of 41 kPa and an elongation at break of 534%.
FIG. 6 is an EIS curve of the PAM-Lap-2 composite hydrogel electrolyte, and the ion conductivity of the PAM-Lap-2 composite hydrogel electrolyte calculated by a fitting circuit is 11.6 mS cm-1。
FIG. 7 is a graph of Zn// Zn symmetric cell voltage vs. time at 0.5 mA cm for PAM-Lap-2-2At a current density of Zn// PAM-Lap-2// Zn the symmetric cell showed a potential rise after 1800 hours, indicating that unstable zinc plating/dissolution began to occur.
Example 2
The steps are the same as example 1, only the amount of the hectorite and the amount of the acrylamide monomer are changed into 100 mg and 1900 mg, and other conditions are not changed, so that the PAM-Lap-3 composite hydrogel is finally obtained.
The zinc-manganese dioxide electrolyte is used as an electrolyte for calculating the ionic conductivity of an ss/ss symmetric battery, is used for representing the inhibition effect on zinc dendrites of a Zn/Zn symmetric battery, and is applied to Zn-MnO2Battery systems and flexible battery systems characterize their applicability.
FIG. 8 is an optical image of the PAM-Lap-3 composite hydrogel electrolyte when twisted, showing its flexibility.
FIG. 9 is an optical picture of the PAM-Lap-3 composite hydrogel electrolyte when stretched, showing its elasticity.
FIG. 10 is an optical picture of self-repair of PAM-Lap-3 composite hydrogel electrolyte, which shows the self-repair performance.
FIG. 11 is a scanning electron microscope image of the PAM-Lap-3 composite hydrogel after being dried, and the composite material is in a porous and lamellar distribution structure.
FIG. 12 is a stress-strain curve of a PAM-Lap-3 composite hydrogel electrolyte, PAM-Lap-3 having a tensile strength of 45kPa and an elongation at break of 606%, indicating that it has excellent mechanical properties.
FIG. 13 is an EIS curve of the PAM-Lap-3 composite hydrogel electrolyte, and the ionic conductivity of the PAM-Lap-3 composite hydrogel electrolyte is 20.7 mS cm calculated by a fitting circuit-1。
FIG. 14 is a timing current curve (inset is EIS before and after polarization) of PAM-Lap-3 composite hydrogel electrolyte applied to Zn// Zn symmetric cell, and the ion transfer number of the composite hydrogel electrolyte is 0.54, which is obtained through calculation, and the high ion transfer number is beneficial to the electrochemical performance of the zinc ion cell.
FIG. 15 shows Zn// Z corresponding to PAM-Lap-3Voltage-time curve of n-symmetric cell at 0.5 mA cm-2At a current density of (a), the Zn// PAM-Lap-3// Zn symmetric cell showed a consistent low voltage polarization of less than 60 mV over 2000 hours, indicating a stable zinc plating/dissolution process.
FIG. 16 is a scanning electron microscope image of a zinc sheet obtained after the PAM-Lap-3 composite hydrogel electrolyte is applied to a Zn// Zn symmetric battery and circulates for 800 hours, the surface of the zinc sheet is not obviously damaged and is deposited along a certain direction, and the PAM-Lap-3 composite hydrogel electrolyte effectively inhibits the growth of zinc dendrites.
FIG. 17 shows the application of PAM-Lap-3 composite hydrogel electrolyte to Zn-MnO2@8% rGO battery system, exhibiting excellent rate performance.
FIG. 18 shows the application of PAM-Lap-3 composite hydrogel electrolyte to Zn-MnO2@8% rGO battery system, at 2A g-1After 2000 times of circulation under high current density, the product still maintains 97 mAh g-1Specific discharge capacity of (2).
FIG. 19 shows that the PAM-Lap-3 composite hydrogel electrolyte shows excellent damage resistance when applied to a flexible battery system.
Fig. 20 shows that the PAM-Lap-3 composite hydrogel electrolyte is applied to a flexible battery system, and can stably supply power to an electronic display due to the stability of the flexible battery system when being bent.
Example 3
The steps are the same as the example 1, only the amount of the hectorite and the amount of the acrylamide monomer are changed into 200 mg and 1800 mg, and other conditions are not changed, so that the PAM-Lap-4 composite hydrogel is finally obtained.
The zinc/iron complex is used as an electrolyte and applied to a ss/ss symmetric battery to calculate the ionic conductivity, and is applied to a Zn/Zn symmetric battery to represent the inhibition effect on zinc dendrites.
FIG. 21 is a stress-strain curve of a PAM-Lap-4 composite hydrogel electrolyte, PAM-Lap-4 having a tensile strength of 44 kPa and an elongation at break of 487%
FIG. 22 is an EIS curve of the PAM-Lap-4 composite hydrogel electrolyte, and the ionic conductivity of the PAM-Lap-4 composite hydrogel electrolyte calculated by a fitting circuit is 17.4 mS cm-1。
FIG. 23 is a voltage-time curve of a Zn// Zn symmetric cell corresponding to the PAM-Lap-4 gel electrolyte in example 4.
Example 4
The steps are the same as example 1, only the amount of the hectorite and the amount of the acrylamide monomer are changed into 300 mg and 1700 mg, and other conditions are not changed, so that the PAM-Lap-5 composite hydrogel is finally obtained.
Example 5
The steps are the same as example 1, only the amount of hectorite and the amount of acrylamide monomer are changed into 600 mg and 1400 mg, and other conditions are not changed, so that the PAM-Lap-6 composite hydrogel is finally obtained.
Example 6
The steps are the same as example 1, only the amount of the hectorite and the amount of the acrylamide monomer are changed to 800 mg and 1200 mg, and other conditions are not changed, so that the PAM-Lap-7 composite hydrogel is finally obtained.
Example 7
A preparation method of a gel electrolyte for effectively inhibiting zinc dendrites comprises the following steps:
(1) adding zinc sulfate and manganese sulfate into distilled water, dissolving by ultrasonic wave, and fixing volume in a volumetric flask to obtain 2 mol/L ZnSO4And 0.2 mol/L MnSO4The mixed aqueous solution of (1).
(2) Adding 200 mg of hectorite into 8 ml of electrolyte solution, stirring for a certain time, uniformly dispersing, adding 1800 mg of acrylic acid monomer, and adding 30% NaOH solution for neutralization; stirring is continued for 20-30 minutes. Simultaneously adding 3 mg of N, N-dimethyl bisacrylamide into 1 ml of electrolyte solution, and performing ultrasonic treatment to uniformly disperse the N, N-dimethyl bisacrylamide; 15 mg of ammonium persulfate is also added into 1 ml of electrolyte solution, and ultrasonic dispersion is carried out to be uniform. They were added to a solution of hectorite and acrylamide monomers and stirred for 30 minutes to form a homogeneous polymerization precursor mixture.
(3) And then injecting the precursor mixed solution into a mold with a designed thickness, wrapping the mold with a metal aluminum foil in a dark place, and polymerizing for 1-2 hours at the temperature of 60-80 ℃ to obtain the PAA-Lap composite hydrogel electrolyte.
Example 8
A preparation method of a gel electrolyte for effectively inhibiting zinc dendrites comprises the following steps:
(1) adding zinc sulfate and manganese sulfate into distilled water, dissolving by ultrasonic wave, and fixing volume in a volumetric flask to obtain 2 mol/L ZnSO4And 0.2 mol/L MnSO4The mixed aqueous solution of (1).
(2) 100 mg of hectorite is added into 8 ml of electrolyte solution, after uniform dispersion is carried out for a certain time by stirring, 1900 mg of hexapolyethylene glycol and glycerol are added, and the stirring is continued for 20 to 30 minutes. Simultaneously adding 3.5 mg of divinyl sulfone into 1 ml of electrolyte solution, and performing ultrasonic treatment to uniformly disperse the divinyl sulfone; 10mg of dimethylaminopyridine was also added to 1 ml of the electrolyte solution and uniformly dispersed by ultrasonic. They were added to a solution of hectorite and acrylamide monomers and stirred for 30 minutes to form a homogeneous polymerization precursor mixture.
(3) And then injecting the precursor mixed solution into a mold with a designed thickness, wrapping the mold with a metal aluminum foil in a dark place, and polymerizing for 1-2 hours at the temperature of 60-80 ℃ to obtain the PEG-Lap composite hydrogel electrolyte.
Example 9
A preparation method of a gel electrolyte for effectively inhibiting zinc dendrites comprises the following steps:
(1) adding zinc sulfate and manganese sulfate into distilled water, dissolving by ultrasonic wave, and fixing volume in a volumetric flask to obtain 2 mol/L ZnSO4And 0.2 mol/L MnSO4The mixed aqueous solution of (1).
(2) 200 mg of hectorite is added into 8 ml of electrolyte solution, after being stirred for a certain time and dispersed evenly, 1800 mg of methacrylic acid monomer is added into the electrolyte solution, and the mixture is continuously stirred for 20 to 30 minutes. Simultaneously, 2.5 mg of N, N-dimethyl bisacrylamide is added into 1 ml of electrolyte solution, and the electrolyte solution is subjected to ultrasonic treatment to be uniformly dispersed; 15 mg of potassium persulfate was also added to 1 ml of the electrolyte solution, and uniformly dispersed by ultrasonic. They were added to a solution of hectorite and acrylamide monomers and stirred for 30 minutes to form a homogeneous polymerization precursor mixture.
(3) And then injecting the precursor mixed solution into a mold with a designed thickness, wrapping the mold with metal aluminum foil in a dark place, and polymerizing for 1-2 hours at the temperature of 60-80 ℃ to obtain the PMAA-Lap composite hydrogel electrolyte.
Example 10
A preparation method of a gel electrolyte for effectively inhibiting zinc dendrites comprises the following steps:
(1) adding zinc sulfate and manganese sulfate into distilled water, dissolving by ultrasonic wave, and fixing volume in a volumetric flask to obtain 2 mol/L ZnSO4And 0.2 mol/L MnSO4The mixed aqueous solution of (1).
(2) 100 mg of hectorite is added into 8 ml of electrolyte solution, after uniform dispersion is carried out for a certain time by stirring, 1900 mg of polyvinyl alcohol monomer is added, and the stirring is continued for 20 to 30 minutes. Simultaneously, adding 5 mg of epoxy chloropropane into 1 ml of electrolyte solution, and performing ultrasonic treatment to uniformly disperse the epoxy chloropropane; adding into the solution of hectorite and acrylamide monomer, stirring for 30 min to obtain a uniform polymer precursor mixture.
(3) And then injecting the precursor mixed solution into a mold with a designed thickness, wrapping the precursor mixed solution with a metal aluminum foil in a dark place, and polymerizing for 1-2 hours at the temperature of 60-80 ℃ to obtain the PVA-Lap composite hydrogel electrolyte.

Claims (8)

1. A gel electrolyte effective in inhibiting zinc dendrites, the gel electrolyte comprising: electrolyte solutions, polymer hydrogels, hectorites; specifically, the hectorite is added in the formation process of the polymer hydrogel after being uniformly mixed in the electrolyte solution.
2. The gel electrolyte effective in suppressing zinc dendrites of claim 1 wherein said polymer hydrogel is: one of polyacrylic acid, polyethylene glycol, polyvinyl alcohol and polymethacrylic acid hydrogel; the electrolyte solution is as follows: zinc sulfate, distilled water and manganese sulfate.
3. The gel electrolyte effective in suppressing zinc dendrites of claim 1 or 2 wherein the starting materials of the polymer hydrogel comprise a polymer monomer, an initiator, a cross-linking agent;
the polymer monomers are: acrylic acid, methacrylic acid or acrylamide, an initiator is ammonium persulfate or potassium persulfate, and a cross-linking agent is N, N-methylene-bisacrylamide;
the polymer monomers are: hexapolyethylene glycol and glycerol, wherein the initiator is dimethylaminopyridine, and the cross-linking agent is divinyl sulfone;
the polymer monomers are: polyvinyl alcohol, initiator NaOH and cross-linking agent epichlorohydrin.
4. The gel electrolyte of claim 1, wherein the laponite is added in an amount of 0.1% to 40% by mass of the electrolyte solution.
5. The gel electrolyte capable of effectively suppressing zinc dendrites of claim 3 wherein the mass ratio of hectorite to polymer monomer is: 40-800:1200-1960.
6. The method of preparing a gel electrolyte effective in suppressing zinc dendrites of claim 1 comprising the steps of:
(1) preparation of electrolyte solution: zinc sulfate, distilled water and manganese sulfate are mixed to prepare the zinc sulfate-manganese sulfate water-based paint;
(2) preparation of polymerization precursor mixture: adding hectorite into a part of electrolyte solution, uniformly dispersing, adding a polymer monomer, and continuously stirring to obtain a solution 1; meanwhile, adding a cross-linking agent into a part of electrolyte solution, and uniformly dispersing to obtain a solution 2; adding an initiator into the rest electrolyte solution, and uniformly dispersing to obtain a solution 3; adding the solution 2 and the solution 3 into the solution 1 to form a uniform polymerization precursor mixed solution;
(3) polymerization of the composite gel electrolyte: and injecting the polymerization precursor mixed solution into a mold, wrapping the mixture with a metal aluminum foil in the dark, and polymerizing for 1-3 h at the temperature of 60-80 ℃ to obtain the polymer-Lap composite hydrogel electrolyte.
7. The production method according to claim 6, wherein the electrolyte solution of the step (1) is 2 mol/L ZnSO4And 0.2 mol/L MnSO4The mixed aqueous solution of (1).
8. Use of the gel electrolyte effective in inhibiting zinc dendrites of claim 1 in an aqueous zinc ion battery.
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