CN113206283A - Aqueous zinc ion battery electrolyte based on eutectic salt electrolyte - Google Patents
Aqueous zinc ion battery electrolyte based on eutectic salt electrolyte Download PDFInfo
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- CN113206283A CN113206283A CN202110486705.9A CN202110486705A CN113206283A CN 113206283 A CN113206283 A CN 113206283A CN 202110486705 A CN202110486705 A CN 202110486705A CN 113206283 A CN113206283 A CN 113206283A
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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
- H01M10/02—Details
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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
- H01M10/36—Accumulators not provided for in groups H01M10/05-H01M10/34
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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
- H01M2300/00—Electrolytes
- H01M2300/0002—Aqueous electrolytes
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- 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
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Abstract
The invention discloses a water-based zinc ion battery electrolyte based on eutectic salt electrolyte, belonging to the technical field of batteries. The eutectic salt is a eutectic system of zinc salt, strong polar neutral ligand and water. The addition of water into the eutectic salt can significantly reduce the viscosity of the electrolyte and improve the ionic conductivity of the electrolyte, and simultaneously promote the uniform nucleation and deposition of the metal zinc. The aqueous electrolyte enables the zinc cathode to have good cycle reversibility and stability, and improves the electrochemical performance of the aqueous zinc ion battery. The water-based zinc ion battery electrolyte disclosed by the invention is low in price, environment-friendly, suitable for industrial production and has a potential application prospect in the field of large-scale energy storage.
Description
Technical Field
The invention belongs to the technical field of water-based batteries, and particularly relates to a water-based zinc ion battery electrolyte based on eutectic salt electrolyte.
Background
With the social development and the innovation of new energy systems, the service field oriented to the secondary power supply gradually shifts from the field of electronic consumer products to the field of large-scale energy storage. The zinc ion battery is considered to be an ideal substitute for the lithium ion battery in the field of large-scale energy storage due to the characteristics of abundant reserves, friendly price and the like. The electrolyte serves as a medium for ion transmission, and is a bridge connecting the positive electrode and the negative electrode, and has a crucial influence on the performance of the battery. Compared with organic electrolyte, the aqueous electrolyte has the advantages of low cost, no pollution, simple preparation process, high safety and the like, and is the most widely applied electrolyte system in the zinc ion battery. The water system electrolyte has high ionic conductivity and low viscosity, and zinc ions have a faster reaction kinetic process in an electrochemical reaction, so that most water system zinc ion batteries have good rate performance. But conventional aqueous electrolytes, e.g. ZnSO4And Zn (CF)3SO3)2The aqueous solution has narrow electrochemical stability window and strong reaction activity, and can generate inevitable hydrogen evolution and oxygen evolution phenomena in the charging and discharging processes, thereby causing serious damage to electrodes, particularly metal zinc cathodes. The zinc cathode is unevenly deposited in the circulating process, a large amount of byproducts such as zinc oxide and the like can be formed on the surface of the zinc cathode, the circulating stability of the battery is reduced, and even the battery can be short-circuited to bring serious potential safety hazards. The electrochemical performance of the aqueous zinc ion battery needs to be further improved.
The selection of high-concentration 'water-in-salt' electrolyte is a good solution for improving the electrochemical performance of the water-based battery. The increase of the salt concentration can reduce the water molecular activity in the system, thereby widening the electrochemical window of the electrolyte, inhibiting hydrogen evolution and improving the coulomb efficiency of the battery. However, the selection of the high-solubility zinc salt is relatively limited, and the increase of the salt concentration can increase the cost of the electrolyte, which is not beneficial to large-scale popularization. Therefore, it is important to develop a novel water-based zinc ion battery electrolyte with low cost and environmental friendliness.
Disclosure of Invention
The invention aims to solve the problems of narrow electrochemical window, unstable zinc cathode and the like of the existing water-based zinc ion battery, and provides a novel water-based zinc ion battery electrolyte based on eutectic salt electrolyte. The electrolyte provided by the invention consists of zinc salt, organic neutral ligand and water, and can remarkably widen the electrochemical window of the electrolyte and promote uniform nucleation and deposition of metal zinc. The zinc ion battery based on the electrolyte shows good cycle stability.
Technical scheme of the invention
A novel aqueous zinc ion battery electrolyte based on eutectic salt electrolyte. The electrolyte is a eutectic system of zinc salt, strong polar neutral ligand and water.
The zinc salt is ZnCl2、Zn(ClO4)2Or Zn (TFSI)2One of (1); the strong polar neutral ligand is one of acetamide, succinonitrile or dimethyl sulfone.
The molar ratio of the zinc salt to the neutral ligand in the electrolyte is 1: 3.
The molar ratio of water to zinc salt in the electrolyte is 1-6.
The invention has the advantages and beneficial effects that:
according to the invention, by introducing water molecules into the eutectic system, the viscosity of the electrolyte is obviously reduced, the ionic conductivity of the electrolyte is improved, and the water-based electrolyte is endowed with the characteristics. Meanwhile, because the water content is lower, the original eutectic salt network in the system is preserved, and the system stability is higher. The prepared electrolyte has certain properties of high-concentration salt and ionic liquid. By introducing water molecules, the uniform nucleation and deposition of the metal zinc are promoted, and the reversibility and the circulation stability of the zinc cathode are improved. The electrolyte is applied to a zinc ion battery and shows excellent electrochemical performance. The water system electrolyte disclosed by the invention is low in cost, environment-friendly and simple in preparation process, is suitable for industrial production, and has potential application prospects in the field of large-scale energy storage.
Drawings
FIG. 1 is a ZnCl-based catalyst of example 12-acetamide aqueous electrolyteThe electrochemical performance of the zinc/phenazine full cell under the current density of 10 ℃;
FIG. 2 is a ZnCl-based catalyst obtained in example 22Electrochemical performance of zinc/phenazine full cells of succinonitrile aqueous electrolyte at 10C current density;
FIG. 3 is a ZnCl-based catalyst in example 32Electrochemical performance at 10C current density of zinc/phenazine full cell of dimethyl sulfone aqueous electrolyte;
FIG. 4 is a graph based on Zn (ClO) in example 44)2Electrochemical performance at 10C current density of zinc/phenazine full cell of dimethyl sulfone aqueous electrolyte;
FIG. 5 is a graph based on Zn (ClO) in example 54)2Electrochemical performance of zinc/phenazine full cells at 10C current density of an acetamide aqueous electrolyte.
Detailed Description
Example 1:
the embodiment provides a preparation method of an aqueous zinc ion battery electrolyte based on a eutectic salt electrolyte, which comprises the following steps: ZnCl2Acetamide and water. Reacting ZnCl2Mixing with acetamide solid at a molar ratio of 1:3, stirring at 80 deg.C for 2 hr until all solids become clear transparent liquid, cooling to room temperature, adding water and ZnCl2Deionized water is added into the mixture according to the molar ratio of 1:1, and the mixture is continuously stirred for 2 hours to prepare aqueous electrolyte.
A small amount of prepared water-based electrolyte is taken, a zinc foil is taken as a negative electrode, phenazine is taken as a positive electrode, Glass fiber is taken as a diaphragm to assemble the full cell, and the electrochemical performance of the full cell is tested under the condition that the multiplying power is 10C current density.
The test results are shown in fig. 1, and the battery still has 85.7 percent capacity retention rate after being stably cycled for 10000 circles with coulombic efficiency close to 100 percent.
Example 2
The embodiment provides a preparation method of an aqueous zinc ion battery electrolyte based on a eutectic salt electrolyte, which comprises the following steps: ZnCl2Succinonitrile and water. Reacting ZnCl2Mixing succinonitrile solid and deionized water at a molar ratio of 1:3:6, stirring at 80 deg.C for 2 hours until all solids become liquidAnd cooling to room temperature, and stirring for 2 hours to prepare the aqueous electrolyte.
A small amount of prepared water-based electrolyte is taken, a zinc foil is taken as a negative electrode, phenazine is taken as a positive electrode, Glass fiber is taken as a diaphragm to assemble the full cell, and the electrochemical performance of the full cell is tested under the condition that the multiplying power is 10C current density.
The test results are shown in fig. 2, and the cell still has a capacity retention of 91.4% after 1000 cycles of stable cycling at a coulombic efficiency close to 100%.
Example 3
The embodiment provides a preparation method of an aqueous zinc ion battery electrolyte based on a eutectic salt electrolyte, which comprises the following steps: ZnCl2Dimethyl sulfone and water. Reacting ZnCl2Mixing the dimethyl sulfone solid and deionized water according to the mol ratio of 1:3:6, stirring for 2 hours at 80 ℃ until all the solid becomes liquid, cooling to room temperature, and then continuously stirring for 2 hours to prepare the water-based electrolyte.
A small amount of prepared water-based electrolyte is taken, a zinc foil is taken as a negative electrode, phenazine is taken as a positive electrode, Glass fiber is taken as a diaphragm to assemble the full cell, and the electrochemical performance of the full cell is tested under the condition that the multiplying power is 10C current density.
The test results are shown in fig. 3, and the cell still has a capacity retention of 84.9% after 650 cycles of stable cycling at a coulombic efficiency close to 100%.
Example 4
The embodiment provides a preparation method of an aqueous zinc ion battery electrolyte based on a eutectic salt electrolyte, which comprises the following steps: zn (ClO)4)2·6H2O and dimethyl sulfone, water in the electrolyte is derived from Zn (ClO)4)2·6H2Water of crystallization in O. Adding Zn (ClO)4)2·6H2Mixing O and dimethyl sulfone solid according to a molar ratio of 1:3, stirring at 80 ℃ for 2 hours until all the solid becomes liquid, cooling to room temperature, and then continuing stirring for 2 hours to prepare the water-based electrolyte.
A small amount of prepared water-based electrolyte is taken, a zinc foil is taken as a negative electrode, phenazine is taken as a positive electrode, Glass fiber is taken as a diaphragm to assemble the full cell, and the electrochemical performance of the full cell is tested under the condition that the multiplying power is 10C current density.
The test results are shown in fig. 4, and the cell still has a capacity retention of 95.5% after 750 cycles of stable cycling at a coulombic efficiency close to 100%.
Example 5
The embodiment provides a preparation method of an aqueous zinc ion battery electrolyte based on a eutectic salt electrolyte, which comprises the following steps: zn (ClO)4)2·6H2O and acetamide, water in the electrolyte is from Zn (ClO)4)2·6H2Water of crystallization in O. Adding Zn (ClO)4)2·6H2Mixing O and acetamide solid according to a molar ratio of 1:3, stirring at 80 ℃ for 2 hours until all the solid becomes liquid, cooling to room temperature, and then continuing stirring for 2 hours to prepare an aqueous electrolyte.
A small amount of prepared water-based electrolyte is taken, a zinc foil is taken as a negative electrode, phenazine is taken as a positive electrode, Glass fiber is taken as a diaphragm to assemble the full cell, and the electrochemical performance of the full cell is tested under the condition that the multiplying power is 10C current density.
The test results are shown in fig. 5, and the cell still has a capacity retention of 93.8% after 500 cycles of stable cycling at a coulombic efficiency close to 100%.
Claims (5)
1. The water-based zinc ion battery electrolyte based on the eutectic salt electrolyte is characterized in that the electrolyte is a eutectic system of zinc salt, strong polar neutral ligand and water.
2. The aqueous zinc ion battery electrolyte based on a eutectic salt electrolyte of claim 1, wherein the strongly polar neutral ligand is one of acetamide, succinonitrile or dimethylsulfone.
3. The aqueous zinc-ion battery electrolyte based on a eutectic salt electrolyte of claim 1, wherein the zinc salt is any one of: ZnCl2、Zn(ClO4)2Or Zn (TFSI)2。
4. The aqueous zinc ion battery electrolyte based on a eutectic salt electrolyte of claim 1, characterized in that the molar ratio of zinc salt to strongly polar neutral ligand is 1: 3.
5. The aqueous zinc ion battery electrolyte based on a eutectic salt electrolyte according to claim 1, wherein the molar ratio of water in the electrolyte to the zinc salt in the eutectic salt electrolyte is 1 to 6.
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| CN202110486705.9A CN113206283A (en) | 2021-05-01 | 2021-05-01 | Aqueous zinc ion battery electrolyte based on eutectic salt electrolyte |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114122535A (en) * | 2022-01-25 | 2022-03-01 | 长沙理工大学 | Zinc ion eutectic salt electrolyte, battery adopting same and preparation method thereof |
| CN115149014A (en) * | 2022-07-13 | 2022-10-04 | 中南大学 | Quasi-deep eutectic electrolyte, application thereof in water system zinc-manganese battery and battery |
Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20060121355A1 (en) * | 2004-12-02 | 2006-06-08 | Vladimir Kolosnitsyn | Electrolyte for lithium-sulphur batteries and lithium-sulphur batteries using the same |
| CN103959172A (en) * | 2012-11-21 | 2014-07-30 | 戴纳洛伊有限责任公司 | Process for removing substances from substrates |
| CN107579291A (en) * | 2017-08-30 | 2018-01-12 | 中国科学院宁波材料技术与工程研究所 | A kind of aqueous electrolyte and Water based metal ion battery |
| CN107768741A (en) * | 2017-09-18 | 2018-03-06 | 中国科学院青岛生物能源与过程研究所 | Eutectic electrolyte and its application in secondary zinc battery |
| US20180309125A1 (en) * | 2017-04-20 | 2018-10-25 | Auburn University | Electrochemical systems comprising mxenes and max phase compositions and methods of using the same |
| CN111261426A (en) * | 2018-12-03 | 2020-06-09 | 深圳新宙邦科技股份有限公司 | Super capacitor electrolyte and super capacitor |
| CN111490240A (en) * | 2020-04-16 | 2020-08-04 | 中国科学院宁波材料技术与工程研究所 | Aqueous lithium ion battery and application thereof |
| CN111540963A (en) * | 2020-05-21 | 2020-08-14 | 中国科学院青岛生物能源与过程研究所 | Water-fused-salt-based zinc electrolyte and application thereof in secondary zinc battery |
-
2021
- 2021-05-01 CN CN202110486705.9A patent/CN113206283A/en active Pending
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20060121355A1 (en) * | 2004-12-02 | 2006-06-08 | Vladimir Kolosnitsyn | Electrolyte for lithium-sulphur batteries and lithium-sulphur batteries using the same |
| CN103959172A (en) * | 2012-11-21 | 2014-07-30 | 戴纳洛伊有限责任公司 | Process for removing substances from substrates |
| US20180309125A1 (en) * | 2017-04-20 | 2018-10-25 | Auburn University | Electrochemical systems comprising mxenes and max phase compositions and methods of using the same |
| CN107579291A (en) * | 2017-08-30 | 2018-01-12 | 中国科学院宁波材料技术与工程研究所 | A kind of aqueous electrolyte and Water based metal ion battery |
| CN107768741A (en) * | 2017-09-18 | 2018-03-06 | 中国科学院青岛生物能源与过程研究所 | Eutectic electrolyte and its application in secondary zinc battery |
| CN111261426A (en) * | 2018-12-03 | 2020-06-09 | 深圳新宙邦科技股份有限公司 | Super capacitor electrolyte and super capacitor |
| CN111490240A (en) * | 2020-04-16 | 2020-08-04 | 中国科学院宁波材料技术与工程研究所 | Aqueous lithium ion battery and application thereof |
| CN111540963A (en) * | 2020-05-21 | 2020-08-14 | 中国科学院青岛生物能源与过程研究所 | Water-fused-salt-based zinc electrolyte and application thereof in secondary zinc battery |
Non-Patent Citations (1)
| Title |
|---|
| JINQIANG SHI ETAL.: ""Water-in-Deep Eutectic Solvent" Electrolytes for High-Performance Aqueous Zn-Ion Batteries", 《ADVANCED FUNCTIONAL MATERIALS》 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114122535A (en) * | 2022-01-25 | 2022-03-01 | 长沙理工大学 | Zinc ion eutectic salt electrolyte, battery adopting same and preparation method thereof |
| CN114122535B (en) * | 2022-01-25 | 2022-06-14 | 长沙理工大学 | Zinc ion eutectic salt electrolyte, battery adopting same and preparation method thereof |
| CN115149014A (en) * | 2022-07-13 | 2022-10-04 | 中南大学 | Quasi-deep eutectic electrolyte, application thereof in water system zinc-manganese battery and battery |
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