CN111261938B - Electrolyte additive for sodium ion battery using prussian blue and analogues thereof as positive electrode material and application of electrolyte additive - Google Patents
Electrolyte additive for sodium ion battery using prussian blue and analogues thereof as positive electrode material and application of electrolyte additive Download PDFInfo
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- CN111261938B CN111261938B CN201811451170.6A CN201811451170A CN111261938B CN 111261938 B CN111261938 B CN 111261938B CN 201811451170 A CN201811451170 A CN 201811451170A CN 111261938 B CN111261938 B CN 111261938B
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- prussian blue
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
- H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
- H01M10/0566—Liquid materials
- H01M10/0567—Liquid materials characterised by the additives
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/054—Accumulators with insertion or intercalation of metals other than lithium, e.g. with magnesium or aluminium
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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
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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
Abstract
The invention discloses an electrolyte additive for a sodium ion battery taking prussian blue and analogues thereof as a positive electrode material and application thereof, belongs to the field of secondary batteries and also belongs to the technical field of energy materials. Compared with a control sample which is not added, the battery using the additive provided by the invention has the advantages that the first discharge capacity is stably improved under the condition that the charge-discharge multiplying power is 1C, the cycle stability is greatly improved, and the cycle capacity retention rate can be improved by 15.1% after 300 cycles.
Description
Technical Field
The invention belongs to the field of secondary batteries and the technical field of energy materials, and particularly relates to an electrolyte additive for a sodium ion battery, which takes prussian blue and analogues thereof as positive electrode materials, and an application thereof.
Background
In recent years, lithium ion batteries have been extensively and deeply researched and developed, and due to the advantages of high energy density, long service life, no memory effect and the like, the lithium ion batteries occupy main markets of portable electronic equipment, electric automobiles and the like, and have great prospects in large-scale energy storage markets. But due to the limited global lithium resource reserves and the high manufacturing cost thereof, the development of the lithium-ion battery in the large-scale energy storage market is severely restricted. Therefore, the novel battery with abundant resource reserves and low cost is researched and developed, and the development challenge of the large-scale energy storage market can be well met. Sodium has the advantages of abundant reserves and low refining cost compared with lithium, and the sodium and the lithium are in the same main group, show similar chemical characteristics and have similar electrode potentials. If a novel sodium ion battery can be researched and developed, the working performance of the battery is enhanced, and the sodium ion battery has a cost advantage over a lithium ion battery in the development of the large-scale energy storage field. For this reason, the research on sodium ion batteries having high capacity and long cycle life has been a hot spot in the field. The Prussian blue and the like are concerned by people due to higher theoretical capacity, but the prepared material contains more bound water, so that the structural stability is severely limited, and the performance of the battery is influenced. The function of the electrolyte is of particular importance for the battery as a whole. At present, the electrolyte used by the sodium ion battery mainly refers to the research results of commercial lithium ion batteries, and carbonate electrolyte is generally used for research, so that further deep research is lacked. Aiming at the electrode materials of Prussian blue and the like, corresponding matching electrolyte is researched and developed, the working performance of the matching electrolyte is exerted to the maximum extent, and the matching electrolyte is an indispensable link for realizing commercialization of the sodium-ion battery in the future.
Disclosure of Invention
In order to solve the problems that when prussian blue and analogues thereof in the prior art are used as the anode material of a sodium ion battery, bound water which is difficult to remove and the surface alkalinity of an electrode material are difficult to remove, water molecules and sodium ions are separated together in the charging and discharging process, the prussian blue type material has a corrupting effect on an electrolyte, and simultaneously, the prussian blue type material is sensitive to the alkaline environment, is easy to be etched by the prussian blue type material and damages the structure of the material, so that the working performance of the battery is greatly and adversely affected, the invention provides an electrolyte additive for the sodium ion battery and application thereof, wherein the prussian blue and analogues thereof are used as the anode material, and the technical scheme is as:
first, the present invention provides an electrolyte additive for sodium ion batteries using prussian blue and the like as a positive electrode material, comprising at least one metal salt having lewis acidity.
The metal salt with Lewis acidity is one or more than two of anhydrous antimony chloride, antimony fluoride, niobium chloride, zinc chloride, tin chloride, chromium chloride, aluminum chloride and titanium chloride.
The invention further provides application of the electrolyte additive for the sodium-ion battery, which takes the Prussian blue and the analogues thereof as the anode material.
The application of the electrolyte additive for the sodium ion battery taking the Prussian blue and the analogues thereof as the anode material is used as the electrolyte additive and added into the basic electrolyte of the sodium ion battery taking the Prussian blue and the analogues thereof as the anode material.
The positive electrode material of the sodium-ion battery is one of Prussian blue and analogues thereof.
The base electrolyte includes a sodium salt and an organic solvent.
The sodium salt comprises NaClO4And NaPF6One or two of them.
The organic solvent is a carbonate organic solvent.
The carbonate organic solvent includes one or more of Ethylene Carbonate (EC), Propylene Carbonate (PC), dimethyl carbonate (DMC), diethyl carbonate (DEC) and fluoroethylene carbonate (FEC).
The electrolyte additive accounts for 0.001-20% of the mass percent of the basic electrolyte.
Advantageous effects
The electrolyte additive disclosed by the invention can neutralize the alkalinity of the surface of electrode materials of Prussian blue and analogues thereof and reduce the etching effect on the electrode materials; meanwhile, in the process of charging and discharging, the bound water of the anode material is removed in the form of hydrated sodium ions, the electrolyte additive can react with the anode material to capture water molecules in the hydrated sodium ions to form a stable compound, and when the anode material is discharged again, the anode material returns to the material in the form of naked sodium ions to play a role in locking the water molecules and consuming the water molecules, can prevent the water molecules under high voltage from decomposing and generating gas, and avoids the phenomenon that the anode material enters the material again in the form of large-size hydrated sodium ions to extrude crystal lattices and damage structures, so that cracks are generated in the circulation process.
The electrolyte additive provided by the invention can better improve the working performance of the battery through the dual functions of neutralizing alkalinity and locking water molecules. Under the condition that the charge-discharge rate is 1C, the first discharge capacity is stably improved, the cycle stability can be greatly improved, and after 300 cycles, the cycle capacity retention rate can be improved by 15.1%.
Drawings
Fig. 1 is a performance curve of the battery prepared in example 1;
fig. 2 is a performance curve of the battery prepared in example 2;
fig. 3 is a performance curve of the battery prepared in example 3.
Detailed Description
Example 1
(1) Preparation of electrolyte
Ethylene Carbonate (EC), diethyl carbonate (DEC) and fluoroethylene carbonate (FEC) were mixed in a volume ratio EC: DEC: FEC of 48:48:4, and sodium perchlorate (NaClO) was added4) Dissolved to a molar concentration of 1 mol/L.
(2) A Prussian blue material is used as a working electrode, a metal sodium sheet is used as a counter electrode, the Prussian blue material and the electrolyte are assembled into a battery to be used as a comparison sample, and the electrochemical performance of the battery is tested.
The addition of the additives provided by the invention:
preparing electrolyte and assembling battery according to the method of the comparative sample, and testing the performance, wherein the difference is as follows: in the electrolyte preparation process, the additive is additionally added for dissolution, and tin chloride is selected as the additive, wherein the addition mass of the tin chloride is 0.5 percent of the mass of the electrolyte.
The test performance curve is shown in figure 1, and it can be seen that, when the charge-discharge rate is 1C, after the additive provided by the invention is added, the first discharge capacity is increased from 104.0mAh/g to 111.8mAh/g, the cycle stability can be greatly increased, and after 300 cycles, the retention rate of the cycle capacity is improved from 75.4% to 82.7%, and is increased by 7.3%.
Example 2
(1) Preparation of electrolyte
Ethylene Carbonate (EC), Propylene Carbonate (PC) and fluoroethylene carbonate (FEC) were mixed at a volume ratio of EC: PC: FEC of 47:47:6, and sodium perchlorate (NaClO4) was added to be dissolved at a molar concentration of 1 mol/L.
(2) A Prussian blue material is used as a working electrode, a metal sodium sheet is used as a counter electrode, the Prussian blue material and the electrolyte are assembled into a battery to be used as a comparison sample, and the electrochemical performance of the battery is tested.
The addition of the additives provided by the invention:
preparing electrolyte and assembling battery according to the method of the comparative sample, and testing the performance, wherein the difference is as follows: in the electrolyte preparation process, the additive is additionally added for dissolution, aluminum chloride is selected as the additive, and the addition mass of the additive is 0.8 percent of the mass of the electrolyte.
The test performance curve is shown in fig. 2, and it can be seen that the first discharge capacity is increased from 104.7mAh/g to 108.2mAh/g under the charge-discharge rate of 1C, and the cycle stability can be greatly improved, after 300 cycles, the cycle capacity retention rate is improved from 81.1% to 93.8%, and is increased by 12.7%.
Example 3
(1) Preparation of electrolyte
Propylene Carbonate (PC) and fluoroethylene carbonate (FEC) were mixed at a volume ratio of PC: FEC of 95:5, and sodium perchlorate (NaClO4) was added to be dissolved at a molar concentration of 1 mol/L.
(2) A Prussian blue material is used as a working electrode, a metal sodium sheet is used as a counter electrode, the Prussian blue material and the electrolyte are assembled into a battery to be used as a comparison sample, and the electrochemical performance of the battery is tested.
The addition of the additives provided by the invention:
preparing electrolyte and assembling battery according to the method of the comparative sample, and testing the performance, wherein the difference is as follows: in the electrolyte preparation process, the additive is additionally added for dissolution, zinc chloride is selected as the additive, and the addition mass of the additive is 1.0 percent of the mass of the electrolyte.
The test performance curve is shown in fig. 3, and it can be seen that the first discharge capacity is increased from 101.4mAh/g to 102.6mAh/g under the charge-discharge rate of 1C, and the cycle stability can be greatly improved, and after 300 cycles, the cycle capacity retention rate is improved from 76.3% to 91.4%, and is increased by 15.1%.
Example 4
(1) Preparation of electrolyte
Ethylene Carbonate (EC), diethyl carbonate (DEC) and fluoroethylene carbonate (FEC) were mixed in a volume ratio EC: DEC: FEC of 48:48:4, and sodium perchlorate (NaClO) was added4) Dissolved to a molar concentration of 1 mol/L.
(2) A Prussian blue material is used as a working electrode, a metal sodium sheet is used as a counter electrode, the Prussian blue material and the electrolyte are assembled into a battery to be used as a comparison sample, and the electrochemical performance of the battery is tested.
The addition of the additives provided by the invention:
preparing electrolyte and assembling battery according to the method of the comparative sample, and testing the performance, wherein the difference is as follows: in the electrolyte preparation process, the additive is additionally added for dissolution, aluminum chloride and titanium chloride are mixed according to the mass ratio of 1:1 to serve as the additive, and the adding mass of the additive is 0.001% of the mass of the electrolyte.
Under the condition that the charge-discharge rate is 1C, after the additive provided by the invention is added, the first discharge capacity is increased from 104.0mAh/g to 105.8mAh/g, the cycle stability can be improved to a certain extent, and after 300 cycles, the cycle capacity retention rate is improved from 75.4% to 77.4%, and is increased by 2.0%.
Example 5
(1) Preparation of electrolyte
Ethylene Carbonate (EC), Propylene Carbonate (PC) and fluoroethylene carbonate (FEC) were mixed at a volume ratio of EC: PC: FEC of 47:47:6, and sodium perchlorate (NaClO4) was added to be dissolved at a molar concentration of 1 mol/L.
(2) A Prussian blue material is used as a working electrode, a metal sodium sheet is used as a counter electrode, the Prussian blue material and the electrolyte are assembled into a battery to be used as a comparison sample, and the electrochemical performance of the battery is tested.
The addition of the additives provided by the invention:
preparing electrolyte and assembling battery according to the method of the comparative sample, and testing the performance, wherein the difference is as follows: in the electrolyte preparation process, the additive is additionally added to dissolve, anhydrous antimony chloride, antimony fluoride and niobium chloride are mixed according to the mass ratio of 1:2:3 to serve as the additive, and the adding mass of the additive is 20% of the mass of the electrolyte.
Under the condition that the charge-discharge rate is 1C, the first discharge capacity is improved from 104.7mAh/g to 107.2mAh/g, the cycle stability can be greatly improved, and after 300 cycles, the cycle capacity retention rate is improved from 81.1 percent to 92.1 percent and is improved by 11.0 percent.
Claims (6)
1. The application of the electrolyte additive for the sodium-ion battery by taking Prussian blue and the analogues thereof as the positive electrode material comprises at least one metal salt with Lewis acidity, wherein the metal salt with Lewis acidity is one or more than two of anhydrous antimony chloride, antimony fluoride, niobium chloride, zinc chloride, tin chloride, chromium chloride, aluminum chloride and titanium chloride, and is characterized in that: the electrolyte additive for the sodium ion battery taking the Prussian blue and the analogues thereof as the anode material is used as an electrolyte additive and is added to and dissolved in the basic electrolyte of the sodium ion battery taking the Prussian blue and the analogues thereof as the anode material.
2. Use according to claim 1, characterized in that: the base electrolyte includes a sodium salt and an organic solvent.
3. Use according to claim 2, characterized in that: the sodium salt comprises NaClO4And NaPF6One or two of them.
4. Use according to claim 2, characterized in that: the organic solvent is a carbonate organic solvent.
5. Use according to claim 4, characterized in that: the carbonate organic solvent includes one or more of Ethylene Carbonate (EC), Propylene Carbonate (PC), dimethyl carbonate (DMC), diethyl carbonate (DEC) and fluoroethylene carbonate (FEC).
6. Use according to claim 1, characterized in that: the electrolyte additive accounts for 0.001-20% of the mass percent of the basic electrolyte.
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| CN201811451170.6A CN111261938B (en) | 2018-11-30 | 2018-11-30 | Electrolyte additive for sodium ion battery using prussian blue and analogues thereof as positive electrode material and application of electrolyte additive |
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| CN201811451170.6A CN111261938B (en) | 2018-11-30 | 2018-11-30 | Electrolyte additive for sodium ion battery using prussian blue and analogues thereof as positive electrode material and application of electrolyte additive |
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| US11876188B2 (en) | 2019-10-29 | 2024-01-16 | Agency For Science, Technology And Research | Electrolyte for use in sodium-sulfur batteries |
| CN114243114A (en) * | 2021-12-28 | 2022-03-25 | 大连中比动力电池有限公司 | Additive and electrolyte for Prussian blue sodium ion battery |
| CN114792843A (en) * | 2022-03-02 | 2022-07-26 | 温州大学碳中和技术创新研究院 | Sodium ion battery high-voltage electrolyte suitable for high-voltage positive electrode material, and preparation method and application thereof |
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