CN115133153A - Aqueous zinc ion electrolyte additive and application thereof - Google Patents

Aqueous zinc ion electrolyte additive and application thereof Download PDF

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Publication number
CN115133153A
CN115133153A CN202210767319.1A CN202210767319A CN115133153A CN 115133153 A CN115133153 A CN 115133153A CN 202210767319 A CN202210767319 A CN 202210767319A CN 115133153 A CN115133153 A CN 115133153A
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China
Prior art keywords
electrolyte
ion battery
zinc ion
aqueous
zinc
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Pending
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CN202210767319.1A
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Chinese (zh)
Inventor
徐彬瑞
王广宾
张紫荷
文博
柳勇
李全安
任凤章
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Henan University of Science and Technology
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Henan University of Science and Technology
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Priority to CN202210767319.1A priority Critical patent/CN115133153A/en
Publication of CN115133153A publication Critical patent/CN115133153A/en
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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
    • H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
    • H01M10/4235—Safety or regulating additives or arrangements in electrodes, separators or electrolyte
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/36—Accumulators not provided for in groups H01M10/05-H01M10/34
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/36—Accumulators not provided for in groups H01M10/05-H01M10/34
    • H01M10/38—Construction or manufacture
    • 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
    • H01M2300/0002—Aqueous electrolytes
    • H01M2300/0005—Acid electrolytes
    • H01M2300/0011—Sulfuric acid-based
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Abstract

The invention relates to a water system zinc ion electrolyte additive and application thereof, belonging to the field of electrochemical energy storage and new energy materials 4 In the electrolyte, an aqueous zinc ion battery having high efficiency and a long life can be produced. The invention greatly promotes the commercial application of the water system zinc ion battery and is helpful for the renewal of an electrochemical energy storage system.

Description

Aqueous zinc ion electrolyte additive and application thereof
Technical Field
The invention belongs to the field of electrochemical energy storage and new energy materials, relates to a water-system zinc ion battery, and particularly relates to a water-system zinc ion electrolyte additive and application thereof.
Background
In recent years, rapid popularization of devices such as mobile communication terminals and electric vehicles has made higher demands for efficient and stable electrochemical energy storage systems. In various battery systems, the most technically mature lithium ion battery has a long cycle life and an ideal weight energy density, and is widely applied. However, the high cost, low safety and environmental issues of lithium ion batteries limit their further development, and the development of new non-lithium electrochemical energy storage systems is urgent.
Compared with an inflammable and toxic organic electrolyte lithium ion battery, the recyclable water system zinc ion battery with zinc as the negative electrode is a novel energy storage system which is low in cost, environment-friendly and safe, and is expected to become a novel battery for replacing the lithium ion battery. The zinc has abundant content on earth, low cost, environment friendliness, and high volume energy density (5855 mAh cm) -3 ). However, although aqueous zinc sulfate solution is often used as a weak acid electrolyte in an aqueous zinc ion battery, dendrite growth and side reactions of the zinc negative electrode in the electrolyte severely limit the life of the aqueous zinc ion battery and also limit the commercialization prospects of the aqueous zinc ion battery. The growth of dendrites not only has serious consequences for the short circuit of the battery, but also causes the formation of "dead zinc" due to the breakage of dendrites. Moreover, during the cycling of the cell, hydrogen evolution reactions occur, which generate large quantities of hydrogen gas, disrupt the cell structure, and produce byproducts.
In order to solve the defects of the above water-based zinc ion battery, researchers have taken various measures, including the construction of a zinc negative electrode protective layer, the research and development of a novel electrolyte, the modification of zinc metal, the selection of a functional electrolyte additive, and the like. Among them, the regulation of the zinc electrode/electrolyte interface by inorganic or organic additives is one of the most effective and simplest methods for suppressing dendrite growth and side reactions. Heretofore, researchers have added small amounts of water-based electrolytesOf metal salts, e.g. Bi + 、Pb + 、Na + 、Li + Salts, and other inorganic compounds such as MXenes, graphene oxide, carbon, and the like. These additives not only inhibit dendrite growth and zinc corrosion, but also inhibit the occurrence of hydrogen evolution reactions. However, the use of heavy metals and expensive materials presents environmental concerns and increased device prices. Recently, many organic additives are also in the field of aqueous zinc ion batteries, some of which may alter the morphology of the zinc deposit, such as polyoxyethylene, polyacrylamide, cetyltrimethylammonium bromide, glucose, etc.
Disclosure of Invention
In order to solve the defects in the prior art, the invention aims at providing the application of a pyridine derivative as an additive of an aqueous zinc ion battery electrolyte, aims at providing an additive for the aqueous zinc ion battery electrolyte, aims at providing an aqueous zinc ion battery electrolyte, and aims at providing an aqueous zinc ion battery. According to the invention, pyridine derivatives such as 2, 4-dihydroxypyridine, 2, 3-dihydroxypyridine or 2-hydroxypyridine are directly added into the prepared ZnSO as additives 4 An aqueous zinc ion battery having high efficiency and long life is produced. The invention greatly promotes the commercial application of the water system zinc ion battery and is helpful for the renewal of an electrochemical energy storage system.
The invention adopts the specific scheme that:
the invention provides an application of a pyridine derivative as an additive of an aqueous zinc ion battery electrolyte. Further, the pyridine derivative is 2, 4-dihydroxypyridine, 2, 3-dihydroxypyridine or 2-hydroxypyridine.
The invention also claims an additive for the electrolyte of the water-based zinc ion battery, wherein the additive is 2, 4-dihydroxypyridine, 2, 3-dihydroxypyridine or 2-hydroxypyridine; the concentration of the 2, 4-dihydroxypyridine in the electrolyte of the water-based zinc ion battery is 1-3 mmol/L; the concentration of the 2, 3-dihydroxypyridine or the 2-hydroxypyridine is 2 mmol/L.
The invention claims an aqueous zinc ion battery electrolyte, and the aqueous zinc ion battery electrolyteThe electrolyte of the sub-battery comprises ZnSO 4 An aqueous electrolyte solution and the above-mentioned additive; the ZnSO 4 The aqueous electrolyte is prepared by mixing ZnSO 4 Dissolving in deionized water to obtain ZnSO 4 The concentration of (A) is 1 mol/L; the additive is dissolved in the ZnSO 4 In an aqueous electrolyte.
The invention further claims an aqueous zinc ion battery, which comprises a positive electrode, a negative electrode, a diaphragm and the aqueous zinc ion battery electrolyte. Preferably, the aqueous zinc ion battery is a Zn/Zn symmetrical battery assembled by taking zinc metal as a negative electrode, glass fiber as a diaphragm, zinc metal as a positive electrode and the aqueous zinc ion battery electrolyte as an electrolyte.
Has the advantages that: the invention takes pyridine derivatives as the additive for the electrolyte of the water-based zinc ion battery, because ZnSO 4 The electrolyte is weakly acidic, and the pyridine additive is alkaline, so that the pyridine additive can be adsorbed at a nucleation site beneficial to zinc in the zinc deposition process, so that zinc ions are promoted to be uniformly deposited to inhibit the generation of zinc dendrites; meanwhile, the water content of the interface between the zinc cathode and the electrolyte can be effectively reduced by the adsorption of the additive, so that the occurrence of hydrogen evolution reaction is also inhibited by the use of the additive. As described above, the use of the pyridine-based additive can suppress the dendritic growth and side reaction on the surface of the zinc negative electrode, thereby improving the cycle life of the aqueous zinc-ion battery.
Drawings
FIG. 1 is a chemical structure diagram of 2, 4-dihydroxypyridine, 2, 3-dihydroxypyridine, and 2-hydroxypyridine;
FIG. 2 is a graph showing the cycle life test of the zinc symmetrical cell of comparative sample and experimental samples 1-3;
FIG. 3 is a graph of the cycle life test of zinc symmetrical cells for comparative and experimental samples 2,4 and 5;
FIG. 4 is a graph of the surface topography of the zinc cathode after the comparative sample and the experimental sample are cycled for 100 cycles;
FIG. 5 is a light microscope photograph of an in situ observation of zinc deposition by an optical microscope;
FIG. 6 is a graph of linear voltammetric sweep tests for the control and experimental samples.
Detailed Description
The invention adopts a pyridine derivative as an electrolyte additive to realize the preparation of the water-based zinc ion battery with high efficiency and long cycle life. The chemical structures of the electrolyte additives for the water-based zinc ion battery are respectively 2, 4-dihydroxypyridine (2, 4-DHP), 2, 3-dihydroxypyridine (2, 3-DHP) and 2-hydroxypyridine (2-DHP) shown in figure 1.
1. Preparing aqueous zinc ion battery electrolyte containing additives.
The method for preparing the aqueous zinc ion battery electrolyte containing the additive comprises the following steps:
(1) 1mol of ZnSO 4 Dissolving in deionized water, shaking to dissolve completely, and making into 1mol/L ZnSO 4 An aqueous electrolyte.
(2) Adding 1-3mmol of 2, 4-dihydroxypyridine into the prepared aqueous electrolyte, and magnetically stirring until the 2, 4-dihydroxypyridine is completely dissolved to prepare the aqueous electrolyte containing the additive.
2. And preparing the water-based zinc ion battery.
1mol/L ZnSO with zinc metal as a negative electrode, glass fiber as a diaphragm and zinc metal as a positive electrode 4 And 2 mmol/L2, 4-dihydroxypyridine-containing aqueous solution is taken as electrolyte to assemble the Zn/Zn symmetrical battery.
Test example: the electrolyte additive of the present invention was evaluated by comparing the control sample with the test sample.
Comparison sample: 1mol/L ZnSO with zinc metal as a negative electrode, glass fiber as a diaphragm and zinc metal as a positive electrode 4 And (4) assembling the Zn/Zn symmetrical battery by taking the aqueous solution as an electrolyte.
Experiment sample 1: 1mol/L ZnSO with zinc metal as a negative electrode, glass fiber as a diaphragm and zinc metal as a positive electrode 4 And the aqueous solution containing 1mmol/L of 2, 4-dihydroxypyridine is taken as electrolyte to assemble the Zn/Zn symmetrical battery.
Experiment sample 2: 1mol/L ZnSO with zinc metal as a negative electrode, glass fiber as a diaphragm and zinc metal as a positive electrode 4 And 2 mmol/L2, 4-dihydroxypyridine-containing aqueous solution is taken as electrolyte to assemble the Zn/Zn symmetrical battery.
Experiment sample 3: using zinc metal as cathode1mol/L ZnSO with glass fiber as diaphragm and zinc metal as anode 4 And the aqueous solution containing 3mmol/L of 2, 4-dihydroxypyridine is taken as electrolyte to assemble the Zn/Zn symmetrical battery.
Experiment sample 4: 1mol/L ZnSO with zinc metal as a negative electrode, glass fiber as a diaphragm and zinc metal as a positive electrode 4 And 2 mmol/L2, 3-dihydroxypyridine-containing aqueous solution is taken as electrolyte to assemble the Zn/Zn symmetrical battery.
Experiment sample 5: 1mol/L ZnSO with zinc metal as a negative electrode, glass fiber as a diaphragm and zinc metal as a positive electrode 4 And 2 mmol/L2-hydroxypyridine-containing aqueous solution is used as electrolyte to assemble the Zn/Zn symmetrical battery.
1. The charge and discharge cycles of the comparative sample and the experimental sample 1 were performed simultaneously, the battery cycle life of the comparative sample was less than 200h, while the battery cycle life of the experimental sample was over 3000h, as shown in fig. 2.
2. The charge and discharge cycles of the comparative sample and the experimental sample 2 were performed simultaneously, the battery cycle life of the comparative sample was less than 200h, while the battery cycle life of the experimental sample was over 5600h, as shown in fig. 2.
3. The charge and discharge cycles of the comparative sample and the experimental sample 3 were performed simultaneously, and the battery cycle life of the comparative sample was less than 200h, while the battery cycle life of the experimental sample was over 400h, as shown in fig. 2.
4. The charge and discharge cycles of the comparative sample and the experimental sample 4 were performed simultaneously, the battery cycle life of the comparative sample was less than 200h, while the battery cycle life of the experimental sample was over 750h, as shown in fig. 3.
5. The charge and discharge cycles of the comparative sample and the experimental sample 5 were performed simultaneously, and the battery cycle life of the comparative sample was less than 200h, while the battery cycle life of the experimental sample was over 800h, as shown in fig. 3.
2. The comparative sample and the experimental sample were circulated for 100 cycles at the same time, the cell was disassembled, and the morphology of the zinc negative electrode was observed by a scanning electron microscope, as shown in fig. 4. By comparison, the zinc deposition on the surface of the zinc cathode is more compact and presents ordered layer-by-layer stacking after the zinc cathode is circulated for 100 circles in the electrolyte with the additive; after 100 circles of circulation in the electrolyte without the additive, zinc deposition on the surface of the zinc cathode is disordered and dead zinc exists.
3. By observing the deposition of zinc in the electrolyte without the 2,4-DHP additive in situ by an optical microscope (fig. 5), it can be found that after 40 minutes, uneven deposition has occurred on the surface of the zinc metal in the electrolyte without the additive, and that after 60 minutes of deposition, dendrites have clearly occurred on the surface of the zinc metal. In contrast, the deposition on the zinc metal surface was always uniform and no dendrites were generated in the electrolyte with additives during the 1 hour deposition.
4. And (3) testing a comparison sample and an experimental sample by using a linear voltammetry scanning method through an electrochemical workstation, so that the strength of the hydrogen evolution reaction on the surface of the zinc cathode can be judged. By comparison (fig. 6), it can be seen that the hydrogen evolution reaction on the surface of the zinc negative electrode is obviously reduced in the electrolyte with the additive.
Through the comparison, 2, 4-dihydroxypyridine, 2, 3-dihydroxypyridine and 2-hydroxypyridine are added into the electrolyte, so that the generation of dendritic crystals and the generation of hydrogen evolution reaction in the zinc deposition process are effectively inhibited, and the cycle life of the battery is obviously prolonged.
It should be noted that the above-mentioned embodiments illustrate rather than limit the scope of the invention, which is defined by the appended claims. It will be apparent to those skilled in the art that certain insubstantial modifications and adaptations of the present invention can be made without departing from the spirit and scope of the invention.

Claims (6)

1. The pyridine derivative is applied as an additive of an electrolyte of an aqueous zinc ion battery.
2. Use according to claim 1, characterized in that: the pyridine derivative is 2, 4-dihydroxypyridine, 2, 3-dihydroxypyridine or 2-hydroxypyridine.
3. An additive for an aqueous zinc ion battery electrolyte, characterized in that: the additive is 2, 4-dihydroxypyridine, 2, 3-dihydroxypyridine or 2-hydroxypyridine; the concentration of the 2, 4-dihydroxypyridine in the electrolyte of the water-based zinc ion battery is 1-3 mmol/L; the concentration of the 2, 3-dihydroxypyridine and the 2-hydroxypyridine in the aqueous zinc ion battery electrolyte is 2 mmol/L.
4. An aqueous zinc ion battery electrolyte characterized in that: the aqueous zinc ion battery electrolyte comprises ZnSO 4 An aqueous electrolyte and the additive of claim 3; the ZnSO 4 The aqueous electrolyte is prepared by mixing ZnSO 4 Dissolving in deionized water to obtain ZnSO 4 The concentration of (A) is 1 mol/L; the additive is dissolved in the ZnSO 4 In an aqueous electrolyte.
5. An aqueous zinc-ion battery characterized in that: an aqueous zinc ion battery electrolyte according to claim 4, comprising a positive electrode, a negative electrode, a separator and the aqueous zinc ion battery electrolyte.
6. The aqueous zinc-ion battery according to claim 5, characterized in that: the aqueous zinc ion battery is a Zn/Zn symmetrical battery assembled by using zinc metal as a negative electrode, glass fiber as a diaphragm and zinc metal as a positive electrode and using the aqueous zinc ion battery electrolyte solution of claim 4 as an electrolyte solution.
CN202210767319.1A 2022-07-01 2022-07-01 Aqueous zinc ion electrolyte additive and application thereof Pending CN115133153A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202210767319.1A CN115133153A (en) 2022-07-01 2022-07-01 Aqueous zinc ion electrolyte additive and application thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202210767319.1A CN115133153A (en) 2022-07-01 2022-07-01 Aqueous zinc ion electrolyte additive and application thereof

Publications (1)

Publication Number Publication Date
CN115133153A true CN115133153A (en) 2022-09-30

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