CN114195935A - Polyanion zinc salt hydrogel electrolyte and zinc battery system - Google Patents

Polyanion zinc salt hydrogel electrolyte and zinc battery system Download PDF

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CN114195935A
CN114195935A CN202010987630.8A CN202010987630A CN114195935A CN 114195935 A CN114195935 A CN 114195935A CN 202010987630 A CN202010987630 A CN 202010987630A CN 114195935 A CN114195935 A CN 114195935A
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zinc salt
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赵金保
丛建龙
曾静
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Xiamen University
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    • 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
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/52—Amides or imides
    • C08F220/54—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide
    • C08F220/58—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide containing oxygen in addition to the carbonamido oxygen, e.g. N-methylolacrylamide, N-(meth)acryloylmorpholine
    • C08F220/585—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide containing oxygen in addition to the carbonamido oxygen, e.g. N-methylolacrylamide, N-(meth)acryloylmorpholine and containing other heteroatoms, e.g. 2-acrylamido-2-methylpropane sulfonic acid [AMPS]
    • 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
    • C08F2/00—Processes of polymerisation
    • C08F2/46—Polymerisation initiated by wave energy or particle radiation
    • C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
    • 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
    • C08F212/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
    • C08F212/34—Monomers containing two or more unsaturated aliphatic radicals
    • C08F212/36—Divinylbenzene
    • 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
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/52—Amides or imides
    • C08F220/54—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide
    • C08F220/58—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide containing oxygen in addition to the carbonamido oxygen, e.g. N-methylolacrylamide, N-(meth)acryloylmorpholine
    • 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
    • H01M6/00—Primary cells; Manufacture thereof
    • H01M6/04—Cells with aqueous electrolyte
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2300/00—Electrolytes
    • H01M2300/0085—Immobilising or gelification of electrolyte
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
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Abstract

The invention discloses a polyanion zinc salt hydrogel electrolyte and a zinc battery system, wherein the electrolyte is an organic zinc salt polymer and is prepared by carrying out polymerization reaction on an organic monomer, zinc salt, a cross-linking agent and an initiator; wherein, the concentration of the organic monomer is 0.1-10 mol/L, and the mass concentration ratio of the organic monomer to the zinc salt is 0.1: 1-10: 1; the organic monomer contains a carbon-carbon double bond and at least one group of sulfonic group, imide group, sulfonimide group, carboxylic group and boric acid group; the zinc salt is a soluble zinc salt. The zinc battery system adopts polyanion zinc salt hydrogel electrolyte, reduces the occurrence of side reaction and inhibits the growth of zinc dendrite by fixing anions in the electrolyte, and realizes the improvement of the electrochemical performance and the cycle stability of the zinc battery system.

Description

Polyanion zinc salt hydrogel electrolyte and zinc battery system
Technical Field
The invention belongs to the technical field of chemical power supplies, and particularly relates to a polyanion zinc salt hydrogel electrolyte and a zinc battery system.
Background
In recent years, Lithium Ion Batteries (LIBs) have been widely used for portable electronic and electric vehicles due to their excellent electrochemical properties. However, safety issues arising from flammable organic electrolytes have driven researchers to develop alternatives to LIBs. Of the various next generation energy storage systems, aqueous zinc-based cells are considered the most promising candidates because zinc metal anodes have unique advantages such as low redox potential (-0.76V versus standard hydrogen electrode), high theoretical capacity (820mAh g)-1And 5855mAh cm-3) Good compatibility with aqueous solution, high safety and environmental protection. However, ZnSO4Severe dendrite formation and side reactions in aqueous solutions (such as hydrogen evolution reactions, zincate formation, etc.) lead to poor cycle life and coulombic efficiency, which have limited the commercial application of zinc-based cells.
To address these problems, researchers have proposed a number of strategies to suppress dendrite formation and mitigate side reactions. An effective method for inhibiting dendrite formation is to construct a modified layer that can modulate ion transport, including TiO2Layer, nano-porous CaCO3Layer, multifunctional brightener layer, zeolite imidazolium salt framework (ZIF-8) layer, etc. In addition, there are also many reported strategies for alleviating side reactions, such as the use of Zn (CF)3SO3)2Electrolyte replacing ZnSO4The electrolyte uses 'water in salt' electrolyte, introduces electrolyte additive, adopts organic electrolyte and solid electrolyte.
However, most of the conventional strategies focus on either the suppression of zinc dendrites or the mitigation of side reactions, and the improvement in performance is limited. In order to obtain a long-life zinc-based battery, it should be considered to achieve high reversibility of the zinc electrode while suppressing zinc dendrites and relieving side reactions.
Disclosure of Invention
The invention aims to overcome the defects of the prior art, provides a polyanion zinc salt hydrogel electrolyte and a zinc battery system, and solves the problem of inhibiting zinc dendrite and side reaction in the background technology.
One of the technical schemes adopted by the invention for solving the technical problems is as follows: provides a polyanion zinc salt hydrogel electrolyte which is prepared by polymerization reaction of an organic monomer, zinc salt, a cross-linking agent and an initiator; wherein, the concentration of the organic monomer is 0.1-10 mol/L, and the mass concentration ratio of the organic monomer to the zinc salt is 0.1: 1-10: 1;
the zinc salt is soluble zinc salt; the organic matter monomer contains carbon-carbon double bonds and at least one group of sulfonic acid group, imide group, sulfonimide group, carboxylic acid group and boric acid group, and H in the group is substituted by zinc ions in polymerization reaction to form an organic acid zinc salt monomer with double bonds.
The second technical scheme adopted by the invention for solving the technical problems is as follows: a zinc battery system is provided, comprising a zinc-containing electrode and the polyanionic zinc salt hydrogel electrolyte.
Compared with the background technology, the technical scheme has the following advantages:
1. according to the scheme, through the domain limiting effect of anions on polyanion chains on zinc ions and the inherent characteristic that polyanion electrolyte has no concentration polarization, the zinc ions can be uniformly deposited and stripped on the surface of the zinc cathode, the growth of zinc dendrites is effectively inhibited, and the cycle life of the battery is prolonged;
2. according to the scheme, polyanion is fixed on the main chain of the zinc salt hydrogel electrolyte, so that the free movement of anions is limited, the free contact with the surface of a zinc cathode is reduced, and the occurrence of side reaction is effectively inhibited;
3. the polyanion zinc salt hydrogel electrolyte adopts a method of in-situ crosslinking and curing in a solution environment in the preparation process, a large amount of solvent (water) is reserved in an electrolyte system, and high ionic conductivity is realized;
4. the electrolyte can be widely applied to a zinc battery system, and has the advantages of simple preparation process, easily obtained raw materials, low cost, safety and reliability.
Drawings
Fig. 1 is an optical photograph of the polyanionic zinc salt hydrogel electrolyte prepared in example 1;
FIG. 2 is a comparison of polarization voltage curves (current density 0.5A/cm) for zinc symmetric cells in example 1 and comparative example 12)；
FIG. 3 is a comparison of the cycling performance of the zinc-copper half cells of example 1 and comparative example 1 (current density 0.5A/g);
FIG. 4 is a comparison of the cycle performance of the zinc-vanadium pentoxide full cells of example 1 and comparative example 1 (current density 0.5A/g).
Detailed Description
In a preferred embodiment of the present invention, the zinc salt is at least one of zinc chloride, zinc acetate, zinc carbonate, zinc nitrate, zinc hydroxide, zinc perchlorate, basic zinc carbonate, zinc trifluoromethanesulfonate, or zinc fluoroborate.
In a preferred embodiment of the present invention, the cross-linking agent comprises borax, boric acid, glutaraldehyde, epichlorohydrin, divinylbenzene, diisocyanate, N-methylenebisacrylamide, and polyethylene glycol (diol) diacrylate. The mass concentration ratio of the cross-linking agent to the organic monomer is 0.01: 100-5: 100.
in a preferred embodiment of the present invention, the initiator comprises lauroyl peroxide, cumene hydroperoxide, dicyclohexyl peroxydicarbonate, potassium persulfate, sodium persulfate, ammonium persulfate, azobisisobutyronitrile, azobisisoheptonitrile, ketoglutaric acid, tert-butyl hydroperoxide/sodium metabisulfite. The mass concentration ratio of the initiator to the organic monomer is 0.01: 100-5: 100.
in a preferred embodiment of the present invention, the organic monomer is 2-acrylamide-2-methylpropanesulfonic Acid (AMPS) or Acrylic Acid (AA).
In a preferred embodiment of the present invention, a zinc battery system comprises a zinc primary battery or a zinc secondary battery, wherein the negative electrode of the zinc-containing electrode is zinc, and the positive electrode comprises zinc, copper, vanadium pentoxide, air, manganese dioxide, prussian blue and derivatives thereof.
Example 1
The polyanionic zinc salt hydrogel electrolyte is prepared by the following steps:
13.6g of AMPS were completely dissolved in 80mL of deionized water at 30 ℃. Then 5g of zinc carbonate is added and dissolved evenly for standby. 0.5g of divinylbenzene, diisocyanate and 0.1g of ketoglutaric acid are dissolved in 80mL of deionized water, and the polyanion zinc salt hydrogel electrolyte is obtained after gamma ray irradiation for 1 h.
In this example, AMPS (structural formula) was used as an organic monomer
Figure BDA0002689775100000041
) H of the middle sulfonic group is substituted by zinc ions in the zinc carbonate to prepare the double-bond organic zinc salt monomer, and the structural formula is as follows:
Figure BDA0002689775100000042
the anionic chain of the polymer formed by polymerizing the double-bond organic acid zinc salt monomer is positioned on the skeleton of the polymer, plays a role in limiting the zinc ions, simultaneously limits the free movement of the anions and reduces the free contact with the surface of the zinc cathode. Fig. 1 is an optical photograph of the polyanionic zinc salt hydrogel electrolyte prepared in example 1, and it can be seen that the prepared electrolyte is typically in the form of a hydrogel.
The polyanionic zinc salt hydrogel electrolyte prepared in the embodiment is respectively assembled into a zinc symmetrical battery, a zinc-copper half battery and a zinc-vanadium pentoxide full battery for carrying out related performance tests:
the test result shows that the zinc symmetrical battery can stably circulate for more than 350h, effectively inhibits the growth of zinc dendrites and has better circulation stability; the zinc-copper half cell can be at 1.0mA/cm2The current density of the reactor is stable for 250 circles, the coulombic efficiency is as high as 98.9 percent, and the side reaction is effectively inhibited; the zinc-vanadium pentoxide full cell can stably run for 200 circles under the current density of 0.5A/g, and the capacity retention rate is 82.4%.
Example 2
Example 2 differs from example 1 in that:
10g of AMPS was completely dissolved in 100mL of deionized water at 80 ℃. Then 5.26g of zinc chloride is added and dissolved evenly for standby. 5g of boric acid, 5.26g of zinc chloride and 0.1g of azobisisobutyronitrile are dissolved in 100mL of deionized water, and heated at 100 ℃ for 2 hours to obtain the polyanionic zinc salt hydrogel electrolyte.
The zinc-air battery is assembled by the polyanionic zinc salt hydrogel electrolyte, the zinc foil and the air anode, 1000 charge-discharge cycles of the obtained zinc-air battery can be realized, and a discharge platform is kept at about 1.5V.
Example 3
Example 3 differs from example 1 in that:
at 70 deg.C, 7.6g of AMPS was completely dissolved in 20mL of deionized water. Then 3g of zinc sulfate is added and dissolved evenly for standby. And dissolving 1g of divinylbenzene in 20mL of deionized water, and reacting for 0.5h under ultraviolet light to obtain the polyanion zinc salt hydrogel electrolyte.
The zinc-manganese dioxide battery is assembled by the polyanionic zinc salt hydrogel electrolyte, the zinc foil and the manganese dioxide positive electrode, the obtained zinc-manganese dioxide battery can be cycled for 200 circles under the current density of 0.1A/g, and the capacity retention rate is 92.3%.
Example 4
Example 4 differs from example 1 in that:
at 70 deg.C, 6g of AMPS was completely dissolved in 40mL of deionized water. Then 1g of zinc perchlorate is added and dissolved evenly for standby. Dissolving 1g N, N-methylene bisacrylamide and 0.3g of potassium persulfate in 40mL of deionized water, and heating at 100 ℃ for 3h to obtain the polyanion zinc salt hydrogel electrolyte.
The polyanionic zinc salt hydrogel electrolyte, the zinc foil and the Prussian blue analogue positive electrode are assembled into the zinc-Prussian blue battery, the obtained zinc-Prussian blue battery can be cycled for 500 circles under the current density of 0.5A/g, and the capacity retention rate is 87.1%.
Comparative example 1
32.2g of ZnSO4Dissolved in 100mL of deionized water, stirred for 5 hours, and then allowed to stand for 24 hours. Obtaining 2.0mol/L ZnSO4And (3) an electrolyte.
This comparative example ZnSO4And respectively assembling the zinc symmetrical battery, the zinc-copper half battery and the zinc-vanadium pentoxide full battery by using the electrolyte.
FIG. 2 shows the hydrogel electrolyte prepared in example 1 filled into a zinc symmetric cell (both positive and negative electrodes are zinc foils) and 2.0mol/L ZnSO prepared in comparative example 14Comparing the performances of zinc symmetrical batteries assembled by electrolyte, and measuring a time-voltage curve (current density is 0.5 mA/cm)2). From FIG. 2, it can be seen that the current density was 0.5mA/cm2When using ZnSO4The zinc symmetrical battery adopting the polyanion zinc salt hydrogel electrolyte can stably circulate for more than 350 hours, effectively inhibits the growth of zinc dendrites and has better circulation stability.
FIG. 3 shows the hydrogel electrolyte prepared in example 1 filled into a zinc-copper half cell and 2.0mol/L ZnSO prepared in comparative example 14The performance of the zinc-copper half cell assembled by electrolyte adopts ZnSO4The coulombic efficiency of the cell adopting the electrolyte drops sharply after 25 circles, while the zinc-copper half cell adopting the polyanion zinc salt hydrogel electrolyte can be 1.0mA/cm2The current density of the reactor is 250 circles, the coulombic efficiency is as high as 98.9 percent, and the side reaction is effectively inhibited.
FIG. 4 shows the hydrogel electrolyte prepared in example 1 charged into a zinc-vanadium pentoxide cell (zinc foil as negative electrode and vanadium pentoxide as positive electrode) and 2.0mol/L ZnSO prepared in comparative example 14The measured capacity retention rate and the change of the number of cycles (current density is 0.5A/g) of the zinc-vanadium pentoxide full battery assembled by the electrolyte. As can be seen from FIG. 4, ZnSO is used4The battery of the electrolyte generates rapid capacity attenuation, and the zinc-vanadium pentoxide full battery adopting the polyanion zinc salt hydrogel electrolyte can stably run for 200 circles under the current density of 0.5A/g, and the capacity retention rate is 82.4%.
Therefore, the zinc battery adopting the polyanion zinc salt hydrogel electrolyte has wide application prospect.
The above examples are only intended to illustrate the technical solution of the present invention, but not to limit it; while the invention has been described in detail and with reference to the foregoing embodiments, it will be understood by those skilled in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some or all of the technical features may be equivalently replaced; and the modifications or the substitutions do not make the essence of the corresponding technical solutions depart from the scope of the technical solutions of the embodiments of the present invention.

Claims (10)

1. A polyanionic zinc salt hydrogel electrolyte, which is characterized in that: prepared by organic monomers, zinc salt, a cross-linking agent and an initiator through polymerization reaction; the zinc salt is soluble zinc salt; the organic matter monomer contains carbon-carbon double bonds and at least one group of sulfonic acid group, imide group, sulfonimide group, carboxylic acid group and boric acid group, and H in the group is substituted by zinc ions in polymerization reaction to form an organic acid zinc salt monomer with double bonds; forming polyanion zinc salt hydrogel after the organic acid zinc salt monomer is polymerized; wherein, the concentration of the organic monomer is 0.1-10 mol/L, and the mass concentration ratio of the organic monomer to the zinc salt is 0.1: 1-10: 1.
2. a polyanionic zinc salt hydrogel electrolyte according to claim 1, wherein said electrolyte comprises: the organic monomer is 2-acrylamide-2-methylpropanesulfonic acid or acrylic acid.
3. A polyanionic zinc salt hydrogel electrolyte according to claim 1, wherein said electrolyte comprises: the zinc salt is at least one of zinc chloride, zinc acetate, zinc carbonate, zinc nitrate, zinc hydroxide, zinc perchlorate, basic zinc carbonate, zinc trifluoromethanesulfonate or zinc fluoroborate.
4. A polyanionic zinc salt hydrogel electrolyte according to claim 1, wherein said electrolyte comprises: the cross-linking agent comprises borax, boric acid, glutaraldehyde, epichlorohydrin, divinylbenzene, diisocyanate, N-methylene bisacrylamide and polyethylene glycol (glycol) diacrylate.
5. A polyanionic zinc salt hydrogel electrolyte according to claim 1, wherein said electrolyte comprises: the mass concentration ratio of the cross-linking agent to the organic monomer is 0.01: 100-5: 100.
6. a polyanionic zinc salt hydrogel electrolyte according to claim 1, wherein said electrolyte comprises: the initiator comprises lauroyl peroxide, cumene hydroperoxide, dicyclohexyl peroxydicarbonate, potassium persulfate, sodium persulfate, ammonium persulfate, azobisisobutyronitrile, azobisisoheptonitrile, ketoglutaric acid and tert-butyl hydroperoxide/sodium metabisulfite.
7. A polyanionic zinc salt hydrogel electrolyte according to claim 1, wherein said electrolyte comprises: the mass concentration ratio of the initiator to the organic monomer is 0.01: 100-5: 100.
8. a zinc battery system, characterized by: comprising a zinc-containing electrode and a polyanionic zinc salt hydrogel electrolyte according to any of claims 1 to 6.
9. A zinc battery system according to claim 8, wherein: the negative electrode of the zinc-containing electrode is zinc, and the positive electrode comprises zinc, copper, vanadium pentoxide, air, manganese dioxide, Prussian blue and derivatives thereof.
10. A zinc battery system according to claim 8, wherein: including zinc primary or secondary batteries.
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CN115275399B (en) * 2022-08-30 2024-05-28 北京理工大学长三角研究院(嘉兴) Electrolyte and aqueous zinc ion battery using same
CN115894788B (en) * 2022-11-09 2023-09-15 电子科技大学长三角研究院(湖州) Multifunctional gel polymer electrolyte and preparation method thereof
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CN114853942A (en) * 2022-05-31 2022-08-05 西北工业大学宁波研究院 Hydrogel electrolyte for zinc-manganese battery and preparation method thereof, and zinc-manganese battery and preparation method thereof
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