CN115621557B - Electrolyte and sodium ion battery - Google Patents
Electrolyte and sodium ion battery Download PDFInfo
- Publication number
- CN115621557B CN115621557B CN202211151983.XA CN202211151983A CN115621557B CN 115621557 B CN115621557 B CN 115621557B CN 202211151983 A CN202211151983 A CN 202211151983A CN 115621557 B CN115621557 B CN 115621557B
- Authority
- CN
- China
- Prior art keywords
- electrolyte
- flake graphite
- sodium
- crystalline flake
- soaking
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Classifications
-
- 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
- H01M10/0568—Liquid materials characterised by the solutes
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G61/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G61/12—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule
- C08G61/122—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule derived from five- or six-membered heterocyclic compounds, other than imides
- C08G61/123—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule derived from five- or six-membered heterocyclic compounds, other than imides derived from five-membered heterocyclic compounds
- C08G61/126—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule derived from five- or six-membered heterocyclic compounds, other than imides derived from five-membered heterocyclic compounds with a five-membered ring containing one sulfur atom in the ring
-
- 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
-
- 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
-
- 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
- H01M2300/0088—Composites
-
- 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 and a sodium ion battery, wherein the electrolyte comprises an electrolyte, an organic solvent and a composite functional additive, the electrolyte is formed by compounding sodium salt and modified crystalline flake graphite, and the mass ratio of the sodium salt to the modified crystalline flake graphite is 10:2-4; the electrolyte accounts for 0.5-5% of the electrolyte by mass, and the composite functional additive accounts for 0.5-10% of the electrolyte by mass. The electrolyte prepared by the invention has the advantages of nonflammability, good thermal stability, high conductivity, wide electrochemical window and the like, can inhibit the generation of sodium dendrite, realizes uniform deposition of sodium, and improves the cycle stability of the battery.
Description
Technical Field
The invention belongs to the technical field of battery materials, and particularly relates to electrolyte and a sodium ion battery.
Background
With the increasing depletion of fossil energy and the rapid development of clean energy such as wind energy and solar energy, the global energy consumption mode will gradually change from fossil energy to new energy. The conversion of the energy consumption mode can depend on advanced large-scale storage technology to a great extent so as to realize safe grid connection of clean energy and efficient and safe utilization of a national power grid. Among various energy storage technologies at present, a commercial lithium ion battery is a relatively mature energy storage technology and has the advantages of high energy density, low self-discharge rate, long service life, convenience in integration and management and the like. However, the reserve of lithium resources in the global crust is low (0.0065%), the regional distribution is uneven (70% is distributed in south america), and the lithium ion battery anode material generally contains expensive transition metal cobalt and the like, so that the lithium ion battery has higher cost. There may be a problem in applying lithium ion batteries to the field of large-scale energy storage. Since sodium and lithium elements are in the same main group and are adjacent to each other, the cost of the sodium ion battery is greatly reduced compared with that of the lithium ion battery, so the sodium ion battery is considered as a potential energy resource of the next generation and becomes a substitute of the most advanced lithium ion battery in the future. The electrochemical equivalent and standard potential of sodium is the most favorable for sodium battery applications following lithium, and sodium ion battery energy storage is gradually beginning to develop in many aspects.
The electrolyte is a key part necessary for normal operation of any battery, plays a role in conducting and conveying current between the anode and the cathode of the battery, and is a bridge for connecting the anode and the cathode materials. In addition, the electrolyte determines the working mechanism of the battery to a great extent, and influences the safety, the multiplying power charge-discharge performance, the specific energy, the cycle performance, the storage performance and the like of the battery. Also, sodium ion batteries are no exception. In sodium ion batteries, the electrolyte not only affects the safety performance of the battery, but also has an important effect on the electrochemical performance of the electrode material, so that improving the electrolyte has an important effect on improving the electrochemical properties of the battery and the material.
At present, sodium ion battery electrolyte mainly uses sodium hexafluorophosphate, sodium tetrafluoroborate, sodium perchlorate and other organic sodium salts as electrolytes, for example, patent application CN105811001A proposes a sodium ion battery electrolyte formula which uses sodium hexafluorophosphate, sodium perchlorate or N-hydroxysulfonyl succinimide sodium as electrolytes, sulfolane and ionic liquid as solvents. When the electrolyte is prepared, the water and oxygen content of the preparation environment needs to be strictly controlled, and the electrolyte needs to be prepared in the environment of less than 0.1 ppm. This patent application uses electrolytes that are very sensitive to water and therefore require strict control of the ambient water oxygen content during processing and addition to the cell, and these electrolytes are relatively complex and costly to manufacture.Patent application CN106030888A proposes a sodium secondary battery excellent in output characteristics, in which the electrolyte formulation is NaPF 6 、NaBF 4 、NaClO 4 、NaAsF 6 、NaSbF 6 、NaN(SO 2 CF 3 ) 2 、NaN(SO 2 C 2 F 5 ) 2 、NaCF 3 SO 3 、NaBC 4 O 8 And the like are electrolytes, and organic solvents such as vinylene carbonate, propylene carbonate, sulfolane and the like are used as main solvents. The electrolyte is similar to the traditional lithium ion battery electrolyte, mainly sodium salt replaces lithium salt, and the formula of the electrolyte is optimized and adjusted to a certain extent. However, in general, the electrolyte which is expensive and very sensitive to the water and oxygen content is not removed, so that the electrolytes are harsh to the operation environment and the application environment, such as common sodium hexafluorophosphate which is very sensitive to the water content and is easy to decompose to generate hydrofluoric acid, and the performance of the battery is deteriorated; sodium perchlorate is prone to potential safety hazards due to its strong oxidizing properties. Therefore, the existing electrolyte is not beneficial to the application and popularization of sodium ion batteries.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide the sodium ion battery electrolyte and the sodium ion battery, wherein the electrolyte has the advantages of nonflammability, good thermal stability, high conductivity, wide electrochemical window and the like, can inhibit the generation of sodium dendrite, realize uniform deposition of sodium and improve the cycling stability of the battery.
In order to achieve the above purpose, the present invention provides the following technical solutions:
the electrolyte comprises electrolyte, an organic solvent and a composite functional additive, wherein the electrolyte is formed by compounding sodium salt and modified crystalline flake graphite, and the mass ratio of the sodium salt to the modified crystalline flake graphite is 10:2-4; the electrolyte accounts for 0.5-5% of the electrolyte by mass, and the composite functional additive accounts for 0.5-10% of the electrolyte by mass.
Preferably, the organic solvent comprises ethylene carbonate, trimethyl phosphate, adiponitrile, 1, 2-tetrafluoroethyl-2, 3-tetrafluoropropyl ether; the mass ratio of the ethylene carbonate to the trimethyl phosphate to the adiponitrile to the 1, 2-tetrafluoroethyl-2, 3-tetrafluoropropyl ether is 30-60:20-40:20-30:10-20.
Preferably, the sodium salt is one or more of sodium triflate, sodium bis (fluorosulfonyl) imide, sodium tetrafluoroborate and sodium bis (oxalato) borate.
Preferably, the preparation method of the modified crystalline flake graphite comprises the following steps:
(1) Adding 5% KMnO into flake graphite 4 Soaking in the water solution for 3-5h, and filtering to obtain pretreated crystalline flake graphite;
(2) Adding the pretreated crystalline flake graphite, thiophene and 1-ethyl- (3-dimethylaminopropyl) carbodiimide in the step (1) into absolute ethyl alcohol, adding ferric chloride under the condition of nitrogen, carrying out in-situ polymerization reaction, and filtering, washing and drying after the reaction is finished to obtain polythiophene/crystalline flake graphite;
(3) Adding the polythiophene/crystalline flake graphite obtained in the step (2) and tin chloride into deionized water, uniformly stirring, soaking, and performing rotary evaporation after soaking to obtain the modified crystalline flake graphite.
Preferably, the mass ratio of the pretreated crystalline flake graphite, thiophene, 1-ethyl- (3-dimethylaminopropyl) carbodiimide and ferric chloride in the step (2) is 20:20-30:5-10:2-5; the polymerization reaction temperature is 30-50 ℃ and the reaction time is 6-10h.
Preferably, in the step (3), the mass ratio of polythiophene to crystalline flake graphite to stannic chloride is 20:1-5; the soaking temperature is 50-60 ℃ and the soaking time is 2-4h.
Preferably, the composite functional additive is prepared by mixing and compounding dimethylacetamide, magnesium oxide and trimethylsilane.
Preferably, the mass ratio of the dimethylacetamide to the magnesium oxide to the trimethylsilane is 10:2-6:5-10.
The invention also protects application of the electrolyte in sodium ion batteries and sodium ion supercapacitors.
The invention also provides a sodium ion battery comprising the electrolyte.
Compared with the prior art, the invention has the following beneficial effects:
(1) According to the sodium ion battery electrolyte provided by the invention, the flake graphite is subjected to immersion oxidation in the potassium permanganate solution to generate more reaction sites on the surface, then thiophene, 1-ethyl- (3-dimethylaminopropyl) carbodiimide and ferric chloride are added for in-situ polymerization reaction to obtain polythiophene/flake graphite, the polythiophene on the flake graphite is modified to enable the graphite to be highly dispersed in the electrolyte, meanwhile, the flake graphite has a lamellar structure and is inserted in the electrolyte, so that the multiplying power performance of the sodium ion battery can be enhanced, and the introduced polythiophene is a conductive polymer and does not influence the conductivity of the flake graphite; finally, tin chloride is coated on the surface of the flake graphite, and SnCl is formed in the circulation process of the sodium metal battery 2 Can be chemically reduced to metallic tin; and spontaneous reaction between metallic tin and metallic sodium generates an in-situ Na-Sn alloy layer and an SEI film rich in NaCl, the double-layer structure is favorable for transferring sodium ions, can obviously reduce polarization voltage, reduce growth of sodium dendrite, and can improve later-stage rate performance and cycle performance of the battery.
(2) According to the sodium ion battery electrolyte provided by the invention, the composite functional additive is added into the electrolyte, and the added dimethylacetamide and trimethylsilane additives have higher stability and weak polarity, so that the electrochemical stability window of the electrolyte can be widened, the compatibility of an electrode and the electrolyte is improved, meanwhile, the added magnesium oxide can play a role in synergistic interaction, the stability of the electrolyte is further enhanced, and the sodium ion battery is enabled to have stronger charge and discharge and cycle performance at high temperature.
(3) The sodium ion battery electrolyte provided by the invention is usually characterized in that the independent ethylene carbonate electrolyte is easy to generate side reaction with a sodium metal negative electrode to form a discontinuous SEI film, so that the enhancement of interface resistance is further caused, and a large amount of dead sodium is generated, so that the solvent is difficult to be independently applied to the sodium metal battery electrolyte; the organic solvent used in the invention is a mixed solvent of ethylene carbonate, trimethyl phosphate, adiponitrile, 1, 2-tetrafluoroethyl-2, 3-tetrafluoropropyl ether, the added trimethyl phosphate has good capability of dissolving sodium salt, the electrochemical stability window is wide, and the electrolyte has good compatibility with modified crystalline flake graphite in the electrolyte, so that a stable SEI layer can be formed on the surface of a negative electrode, and the growth of sodium dendrite is effectively inhibited; adiponitrile and ethylene carbonate can improve the cycle performance of the electrolyte, and 1, 2-tetrafluoroethyl-2, 3-tetrafluoropropyl ether can improve the compatibility of the electrolyte and electrode materials, in particular to carbon-based anode materials, because fluorine has electron-withdrawing effect, solvent molecules can form SEI film on the surface of the negative electrode more easily, so that the electrochemical performance of the battery is improved, and the 1, 2-tetrafluoroethyl-2, 3-tetrafluoropropyl ether has low viscosity, low surface tension and good electrochemical stability; meanwhile, the added trimethyl phosphate, adiponitrile and 1, 2-tetrafluoroethyl-2, 3-tetrafluoropropyl ether have good flame retardance, can play a role in synergistic flame retardance, and improve the flame retardance of the electrolyte.
Detailed Description
The technical solutions of the present invention will be clearly and completely described in connection with the embodiments, and it is obvious that the described embodiments are only some embodiments of the present invention, not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
The flake graphite is purchased from the mineral products limited company of the Jiujiu county, and the mesh number is 325.
Example 1
The electrolyte comprises electrolyte, an organic solvent and a composite functional additive, wherein the electrolyte is formed by compounding sodium triflate and modified crystalline flake graphite, and the mass ratio of the sodium triflate to the modified crystalline flake graphite is 10:3, a step of; the electrolyte accounts for 3% of the electrolyte in mass fraction, and the composite functional additive accounts for 5% of the electrolyte in mass fraction.
Wherein the organic solvent comprises the following components in percentage by mass: 30:25:15, trimethyl phosphate, adiponitrile, 1, 2-tetrafluoroethyl-2, 3-tetrafluoropropyl ether;
the preparation method of the modified crystalline flake graphite comprises the following steps:
(1) Adding 5% KMnO into flake graphite 4 Soaking the aqueous solution for 4 hours, and then filtering to obtain pretreated crystalline flake graphite;
(2) Adding the pretreated crystalline flake graphite (20 g), 27g thiophene and 8g 1-ethyl- (3-dimethylaminopropyl) carbodiimide in the step (1) into 600mL absolute ethyl alcohol, adding 4g ferric chloride under the condition of nitrogen, carrying out in-situ polymerization reaction at the reaction temperature of 45 ℃ for 9 hours, and carrying out filtration, washing and drying treatment after the reaction is completed to obtain polythiophene/crystalline flake graphite;
(3) Adding the polythiophene/crystalline flake graphite (20 g) obtained in the step (2) and 4g of tin chloride into 200mL of deionized water, uniformly stirring, soaking at 55 ℃ for 3 days, and performing rotary evaporation to remove water after soaking to obtain the modified crystalline flake graphite.
The composite functional additive comprises the following components in percentage by mass: 5:8, dimethylacetamide, magnesium oxide and trimethylsilane.
Example 2
The electrolyte comprises an electrolyte, an organic solvent and a composite functional additive, wherein the electrolyte is formed by compounding sodium bis (fluorosulfonyl) imide and modified crystalline flake graphite, and the mass ratio of the sodium bis (fluorosulfonyl) imide to the modified crystalline flake graphite is 10:3, a step of; the electrolyte accounts for 2% of the electrolyte in mass fraction, and the composite functional additive accounts for 3% of the electrolyte in mass fraction.
Wherein the organic solvent comprises the following components in percentage by mass: 30:25:15, trimethyl phosphate, adiponitrile, 1, 2-tetrafluoroethyl-2, 3-tetrafluoropropyl ether;
the preparation method of the modified crystalline flake graphite comprises the following steps:
(1) Adding 5% KMnO into flake graphite 4 Soaking the aqueous solution for 4 hours, and then filtering to obtain pretreated crystalline flake graphite;
(2) Adding the pretreated crystalline flake graphite (20 g), 23g thiophene and 7g 1-ethyl- (3-dimethylaminopropyl) carbodiimide in the step (1) into 600mL absolute ethyl alcohol, adding 3g ferric chloride under the condition of nitrogen, carrying out in-situ polymerization reaction at the reaction temperature of 40 ℃ for 7h, and carrying out filtration, washing and drying treatment after the reaction is finished to obtain polythiophene/crystalline flake graphite;
(3) Adding the polythiophene/crystalline flake graphite (20 g) obtained in the step (2) and 3g of tin chloride into 200mL of deionized water, uniformly stirring, soaking at 55 ℃ for 3 hours, and performing rotary evaporation to remove water after soaking to obtain the modified crystalline flake graphite.
The composite functional additive comprises the following components in percentage by mass: 3:7, dimethylacetamide, magnesium oxide and trimethylsilane.
Example 3
The electrolyte comprises electrolyte, an organic solvent and a composite functional additive, wherein the electrolyte is formed by compounding sodium tetrafluoroborate and modified crystalline flake graphite, and the mass ratio of the sodium tetrafluoroborate to the modified crystalline flake graphite is 10:2; the electrolyte accounts for 0.5% of the electrolyte in mass percent, and the composite functional additive accounts for 0.5% of the electrolyte in mass percent.
Wherein the organic solvent comprises the following components in percentage by mass: 20:20:10, trimethyl phosphate, adiponitrile, 1, 2-tetrafluoroethyl-2, 3-tetrafluoropropyl ether;
the preparation method of the modified crystalline flake graphite comprises the following steps:
(1) Adding 5% KMnO into flake graphite 4 Soaking the aqueous solution for 3 hours, and then filtering to obtain pretreated crystalline flake graphite;
(2) Adding the pretreated crystalline flake graphite (20 g), 20g thiophene and 5g 1-ethyl- (3-dimethylaminopropyl) carbodiimide in the step (1) into 600mL absolute ethyl alcohol, adding 2g ferric chloride under the condition of nitrogen, carrying out in-situ polymerization reaction at the reaction temperature of 30 ℃ for 6 hours, and carrying out filtration, washing and drying treatment after the reaction is finished to obtain polythiophene/crystalline flake graphite;
(3) Adding the polythiophene/crystalline flake graphite (20 g) obtained in the step (2) and 1g of tin chloride into 200mL of deionized water, uniformly stirring, soaking at 50 ℃ for 2 hours, and performing rotary evaporation to remove water after soaking to obtain the modified crystalline flake graphite.
The composite functional additive comprises the following components in percentage by mass: 2:5, the magnesium oxide and the trimethylsilane are mixed and compounded.
Example 4
The electrolyte comprises electrolyte, an organic solvent and a composite functional additive, wherein the electrolyte is formed by compounding sodium bis (oxalato) borate and modified crystalline flake graphite, and the mass ratio of the sodium bis (oxalato) borate to the modified crystalline flake graphite is 10:4, a step of; the electrolyte accounts for 5% of the electrolyte in mass fraction, and the composite functional additive accounts for 10% of the electrolyte in mass fraction.
Wherein the organic solvent comprises the following components in percentage by mass: 40:30:20, trimethyl phosphate, adiponitrile, 1, 2-tetrafluoroethyl-2, 3-tetrafluoropropyl ether;
the preparation method of the modified crystalline flake graphite comprises the following steps:
(1) Adding 5% KMnO into flake graphite 4 Soaking the aqueous solution for 5 hours, and then filtering to obtain pretreated crystalline flake graphite;
(2) Adding the pretreated crystalline flake graphite (20 g), 30g thiophene and 10g 1-ethyl- (3-dimethylaminopropyl) carbodiimide in the step (1) into 600mL absolute ethyl alcohol, adding 5g ferric chloride under the condition of nitrogen, carrying out in-situ polymerization reaction at 50 ℃ for 10 hours, and filtering, washing and drying after the reaction is completed to obtain polythiophene/crystalline flake graphite;
(3) Adding the polythiophene/crystalline flake graphite (20 g) obtained in the step (2) and 5g of tin chloride into 200mL of deionized water, uniformly stirring, soaking at 60 ℃ for 4 hours, and performing rotary evaporation to remove water after soaking to obtain the modified crystalline flake graphite.
The composite functional additive comprises the following components in percentage by mass: 6:10, magnesia and trimethylsilane.
Comparative example 1
An electrolyte, wherein the electrolyte comprises an electrolyte, an organic solvent and a composite functional additive, and the electrolyte is sodium triflate; the electrolyte accounts for 3% of the electrolyte in mass fraction, and the composite functional additive accounts for 5% of the electrolyte in mass fraction.
Wherein the organic solvent comprises the following components in percentage by mass: 30:25:15, trimethyl phosphate, adiponitrile, 1, 2-tetrafluoroethyl-2, 3-tetrafluoropropyl ether;
the composite functional additive comprises the following components in percentage by mass: 5:8, dimethylacetamide, magnesium oxide and trimethylsilane.
The difference between this comparative example and example 1 is that: the electrolyte is not added with modified crystalline flake graphite.
Comparative example 2
The electrolyte comprises electrolyte, an organic solvent and a composite functional additive, wherein the electrolyte is formed by compounding sodium triflate and modified crystalline flake graphite, and the mass ratio of the sodium triflate to the modified crystalline flake graphite is 10:3, a step of; the electrolyte accounts for 3% of the electrolyte in mass fraction, and the composite functional additive accounts for 5% of the electrolyte in mass fraction.
Wherein the organic solvent comprises the following components in percentage by mass: 30, and trimethyl phosphate;
the preparation method of the modified crystalline flake graphite comprises the following steps:
(1) Adding 5% KMnO into flake graphite 4 Soaking the aqueous solution for 4 hours, and then filtering to obtain pretreated crystalline flake graphite;
(2) Adding the pretreated crystalline flake graphite (20 g), 27g thiophene and 8g 1-ethyl- (3-dimethylaminopropyl) carbodiimide in the step (1) into 600mL absolute ethyl alcohol, adding 4g ferric chloride under the condition of nitrogen, carrying out in-situ polymerization reaction at the reaction temperature of 45 ℃ for 9 hours, and carrying out filtration, washing and drying treatment after the reaction is completed to obtain polythiophene/crystalline flake graphite;
(3) Adding the polythiophene/crystalline flake graphite (20 g) obtained in the step (2) and 4g of tin chloride into 200mL of deionized water, uniformly stirring, soaking at 55 ℃ for 3 days, and performing rotary evaporation to remove water after soaking to obtain the modified crystalline flake graphite.
The composite functional additive comprises the following components in percentage by mass: 5:8, dimethylacetamide, magnesium oxide and trimethylsilane.
The difference between this comparative example and example 1 is that: adiponitrile and 1, 2-tetrafluoroethyl-2, 3-tetrafluoropropyl ether are not added into the organic solvent.
Comparative example 3
The electrolyte comprises electrolyte, an organic solvent and a composite functional additive, wherein the electrolyte is formed by compounding sodium triflate and modified crystalline flake graphite, and the mass ratio of the sodium triflate to the modified crystalline flake graphite is 10:3, a step of; the electrolyte accounts for 3% of the electrolyte in mass fraction, and the composite functional additive accounts for 5% of the electrolyte in mass fraction.
Wherein the organic solvent comprises the following components in percentage by mass: 30:25:15, trimethyl phosphate, adiponitrile, 1, 2-tetrafluoroethyl-2, 3-tetrafluoropropyl ether;
the preparation method of the modified crystalline flake graphite comprises the following steps:
(1) Adding 5% KMnO into flake graphite 4 Soaking the aqueous solution for 4 hours, and then filtering to obtain pretreated crystalline flake graphite;
(2) Adding the pretreated crystalline flake graphite (20 g), 27g thiophene and 8g 1-ethyl- (3-dimethylaminopropyl) carbodiimide in the step (1) into 600mL absolute ethyl alcohol, adding 4g ferric chloride under the condition of nitrogen, carrying out in-situ polymerization reaction at the reaction temperature of 45 ℃ for 9 hours, and carrying out filtration, washing and drying treatment after the reaction is completed to obtain polythiophene/crystalline flake graphite;
(3) Adding the polythiophene/crystalline flake graphite (20 g) obtained in the step (2) and 4g of tin chloride into 200mL of deionized water, uniformly stirring, soaking at 55 ℃ for 3 days, and performing rotary evaporation to remove water after soaking to obtain the modified crystalline flake graphite.
The composite functional additive is dimethylacetamide.
The difference between this comparative example and example 1 is that: magnesium oxide and trimethylsilane are not added into the composite functional additive.
The electrolytes prepared in examples 1 to 4 and comparative examples 1 to 3 above were each prepared as follows.
Positive electrode of sodium ion battery: selecting Na 0.9 Cu 0.22 Fe 0.3 Mn 0.48 O 2 As the positive electrode material, positive electrode material Na 0.9 Cu 0.22 Fe 0.3 Mn 0.48 O 2 Carbon Nanotubes (CNTs) and polyvinylidene fluoride (PVDF) in a mass ratio of 97.4:1.3:1.3, coating the mixture on an aluminum foil current collector, drying the aluminum foil current collector through an oven, and rolling the aluminum foil current collector on a roll squeezer to obtain the required positive plate.
Negative electrode of sodium ion battery: hard carbon is selected as a negative electrode material, and the hard carbon, sodium carboxymethyl cellulose (CMC), carbon Nanotubes (CNTs) and Styrene Butadiene Rubber (SBR) are mixed according to the following ratio of 95.8:1.4:0.8:2.0, coating the mixture on an aluminum foil current collector, drying the aluminum foil current collector through an oven, and rolling the aluminum foil current collector on a roll squeezer to obtain the required negative electrode sheet.
Separator of sodium ion battery: a ceramic coated Polyethylene (PE) film was chosen as the barrier film, with a thickness of 2 μm ceramic +12 μm PE +2 μm ceramic.
The performance test was carried out by preparing a small soft pack battery of 2Ah from the pole piece by lamination method, and adding each electrolyte of examples 1-4 and comparative examples 1-3, respectively, and the test results are shown in Table 1 below:
the prepared batteries are respectively subjected to cyclic test at 45 ℃ and-10 ℃, are respectively charged to 4.0 volts at 0.5 ℃ and then are left for 5 minutes; the cell was discharged to 1.5 volts at 0.5C current and left to stand for 5 minutes. Repeating the above steps 400 times to obtain a capacity of the battery after 400 cycles at 0.1C current discharge to 1.5V, and calculating the capacity maintenance rate before and after the cycles from the following formula, wherein the capacity maintenance rate= (400 th cycle discharge capacity/first cycle discharge capacity) ×100%
TABLE 1
As can be seen from the table 1, after the electrolyte provided by the invention is applied to a sodium ion battery, the cycle capacity performance of the electrolyte is obviously improved at 45 ℃ and-10 ℃, and the electrolyte has good application prospect.
Although embodiments of the present invention have been shown and described, it will be understood by those skilled in the art that various changes, modifications, substitutions and alterations can be made therein without departing from the principles and spirit of the invention, the scope of which is defined in the appended claims and their equivalents.
Claims (7)
1. The electrolyte is characterized by comprising electrolyte, an organic solvent and a composite functional additive, wherein the electrolyte is formed by compounding sodium salt and modified crystalline flake graphite, and the mass ratio of the sodium salt to the modified crystalline flake graphite is 10:2-4; the electrolyte accounts for 0.5-5% of the electrolyte, and the composite functional additive accounts for 0.5-10% of the electrolyte;
wherein the organic solvent comprises ethylene carbonate, trimethyl phosphate, adiponitrile, 1, 2-tetrafluoroethyl-2, 3-tetrafluoropropyl ether; the mass ratio of the ethylene carbonate to the trimethyl phosphate to the adiponitrile to the 1, 2-tetrafluoroethyl-2, 3-tetrafluoropropyl ether is 30-60:20-40:20-30:10-20 parts of a base;
the composite functional additive is prepared by mixing and compounding dimethylacetamide, magnesium oxide and trimethylsilane;
the preparation method of the modified crystalline flake graphite comprises the following steps:
(1) Adding 5% KMnO into flake graphite 4 Soaking in the water solution for 3-5h, and filtering to obtain pretreated crystalline flake graphite;
(2) Adding the pretreated crystalline flake graphite, thiophene and 1-ethyl- (3-dimethylaminopropyl) carbodiimide in the step (1) into absolute ethyl alcohol, adding ferric chloride under the condition of nitrogen, carrying out in-situ polymerization reaction, and filtering, washing and drying after the reaction is finished to obtain polythiophene/crystalline flake graphite;
(3) Adding the polythiophene/crystalline flake graphite obtained in the step (2) and tin chloride into deionized water, uniformly stirring, soaking, and performing rotary evaporation after soaking to obtain the modified crystalline flake graphite.
2. An electrolyte according to claim 1, wherein the sodium salt is one or more of sodium triflate, sodium bis (fluorosulfonyl) imide, sodium tetrafluoroborate, sodium bis (oxalato) borate.
3. An electrolyte according to claim 1, wherein the mass ratio of the pretreated flake graphite, thiophene, 1-ethyl- (3-dimethylaminopropyl) carbodiimide, ferric chloride in step (2) is 20:20-30:5-10:2-5; the polymerization reaction temperature is 30-50 ℃ and the reaction time is 6-10h.
4. The electrolyte according to claim 1, wherein the mass ratio of polythiophene to crystalline flake graphite to tin chloride in the step (3) is 20:1-5; the soaking temperature is 50-60 ℃ and the soaking time is 2-4h.
5. The electrolyte according to claim 1, wherein the mass ratio of dimethylacetamide, magnesium oxide and trimethylsilane is 10:2-6:5-10.
6. Use of the electrolyte according to any one of claims 1-5 in sodium ion batteries, sodium ion supercapacitors.
7. A sodium ion battery comprising the electrolyte of any one of claims 1-5.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211151983.XA CN115621557B (en) | 2022-09-21 | 2022-09-21 | Electrolyte and sodium ion battery |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211151983.XA CN115621557B (en) | 2022-09-21 | 2022-09-21 | Electrolyte and sodium ion battery |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN115621557A CN115621557A (en) | 2023-01-17 |
| CN115621557B true CN115621557B (en) | 2023-05-09 |
Family
ID=84858603
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202211151983.XA Active CN115621557B (en) | 2022-09-21 | 2022-09-21 | Electrolyte and sodium ion battery |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN115621557B (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115954551B (en) * | 2023-03-10 | 2023-05-23 | 四川易纳能新能源科技有限公司 | Sodium ion battery electrolyte, preparation method thereof and sodium ion battery |
| CN117117328B (en) * | 2023-10-23 | 2024-01-12 | 深圳华驰新能源科技有限公司 | Electrolyte and lithium ion battery containing same |
Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2001052737A (en) * | 1999-08-10 | 2001-02-23 | Hitachi Maxell Ltd | Nonaqueous electrolyte and nonaqueous electrolyte secondary battery using the same |
| JP2010165674A (en) * | 2008-12-18 | 2010-07-29 | Equos Research Co Ltd | Electrolyte for sodium ion battery |
| JP2014225393A (en) * | 2013-05-17 | 2014-12-04 | パナソニック株式会社 | Sodium secondary battery |
| JP2015079621A (en) * | 2013-10-16 | 2015-04-23 | 三菱化学株式会社 | Composite graphite particle for nonaqueous secondary battery negative electrodes, negative electrode for nonaqueous secondary batteries, and nonaqueous secondary battery |
| KR20160121998A (en) * | 2015-04-13 | 2016-10-21 | 울산과학기술원 | Secondary battery and pouch type secondary battery |
| JP2017224428A (en) * | 2016-06-14 | 2017-12-21 | パナソニックＩｐマネジメント株式会社 | Battery electrolyte solution and battery |
| CN111066192A (en) * | 2017-08-10 | 2020-04-24 | 三菱化学株式会社 | Nonaqueous electrolyte secondary battery |
| CN111564665A (en) * | 2020-05-08 | 2020-08-21 | 广东金光高科股份有限公司 | Ultra-high temperature safety lithium ion battery electrolyte and lithium ion battery using same |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US10854923B2 (en) * | 2017-10-19 | 2020-12-01 | Battelle Memorial Institute | Low flammability electrolytes for stable operation of lithium and sodium ion batteries |
| US11394022B2 (en) * | 2020-04-09 | 2022-07-19 | Uchicago Argonne, Llc | Electroactive materials for secondary batteries |
-
2022
- 2022-09-21 CN CN202211151983.XA patent/CN115621557B/en active Active
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2001052737A (en) * | 1999-08-10 | 2001-02-23 | Hitachi Maxell Ltd | Nonaqueous electrolyte and nonaqueous electrolyte secondary battery using the same |
| JP2010165674A (en) * | 2008-12-18 | 2010-07-29 | Equos Research Co Ltd | Electrolyte for sodium ion battery |
| JP2014225393A (en) * | 2013-05-17 | 2014-12-04 | パナソニック株式会社 | Sodium secondary battery |
| JP2015079621A (en) * | 2013-10-16 | 2015-04-23 | 三菱化学株式会社 | Composite graphite particle for nonaqueous secondary battery negative electrodes, negative electrode for nonaqueous secondary batteries, and nonaqueous secondary battery |
| KR20160121998A (en) * | 2015-04-13 | 2016-10-21 | 울산과학기술원 | Secondary battery and pouch type secondary battery |
| JP2017224428A (en) * | 2016-06-14 | 2017-12-21 | パナソニックＩｐマネジメント株式会社 | Battery electrolyte solution and battery |
| CN111066192A (en) * | 2017-08-10 | 2020-04-24 | 三菱化学株式会社 | Nonaqueous electrolyte secondary battery |
| CN111564665A (en) * | 2020-05-08 | 2020-08-21 | 广东金光高科股份有限公司 | Ultra-high temperature safety lithium ion battery electrolyte and lithium ion battery using same |
Non-Patent Citations (3)
| Title |
|---|
| Zhao, SM等.Synthesis of polythiophene/graphite composites and their enhanced electrochemical performance for aluminum ion batteries.《NEW JOURNAL OF CHEMISTRY》.2019,第43卷(第37期),第15014-15022页. * |
| 闫冬.金属离子掺杂聚噻吩及其纳米复合材料的研究.《中国优秀硕士学位论文全文数据库（工程科技Ⅰ辑）》.2019,(第05期),B016-172. * |
| 黄文达等.F-EPE与LiTFSI联用对LiNi0.5Co0.2Mn0.3O2电池性能的影响.《电池工业》.2018,第22卷(第06期),第291-294页. * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN115621557A (en) | 2023-01-17 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN115621557B (en) | Electrolyte and sodium ion battery | |
| CN107275671A (en) | A kind of electrolyte and preparation method and lithium battery for suppressing Li dendrite | |
| An et al. | Preparation and properties of ionic-liquid mixed solutions as a safety electrolyte for lithium ion batteries | |
| CN103259043A (en) | Lithium ion secondary battery and electrolyte thereof | |
| CN105514378A (en) | Lithium-sulfur battery positive-pole composite material with imitated cellular structure and preparation method thereof | |
| CN105206875A (en) | Electrolyte for improving cycle performance of anode materials of lithium-ion batteries | |
| CN105576241A (en) | Preparation method of silicon/carbon composite material applied to high-performance lithium ion battery anodes | |
| CN113937341A (en) | Metal zinc secondary battery | |
| CN102760881A (en) | Surface-coated natural graphite, preparation method thereof and lithium ion battery | |
| CN112563570A (en) | Lithium ion battery non-aqueous electrolyte of three-salt system and lithium ion battery | |
| CN107706454A (en) | A kind of fluoro-alkyl sulfimide class additive for promoting graphitic carbon negative electrode film forming and the electrolyte containing the additive | |
| CN114447333A (en) | Sodium ion battery | |
| CN113506914A (en) | Ternary lithium ion battery electrolyte and lithium ion battery containing same | |
| Xu et al. | Compatibility of lithium oxalyldifluoroborate with lithium metal anode in rechargeable batteries | |
| Zuo et al. | Effect of NN dimethyltrifluoroacetamide additive on low temperature performance of graphite anode | |
| CN110148774A (en) | Nickelic tertiary cathode material system battery electrolytic solution and lithium ion battery | |
| CN107204485B (en) | A kind of polynary electrolyte of battery capacitor low temperature | |
| CN105428704A (en) | Modified oxidation-reduction type solid electrolyte as well as preparation method and application thereof | |
| CN110718692B (en) | Fluoride stabilizing layer of lithium-sulfur battery, preparation method of fluoride stabilizing layer and lithium-sulfur battery | |
| CN116014073A (en) | Negative electrode plate of sodium ion battery, sodium ion battery and application | |
| CN110767878B (en) | Conductive polymer coated silicon-based negative electrode plate and preparation method and application thereof | |
| CN114094096A (en) | Method for forming protective polymer film on surface of sodium titanium phosphate negative electrode material, product and application thereof | |
| CN106785023A (en) | A kind of lithium ion battery silicon substrate/silicon-carbon composite cathode material electrolyte system | |
| CN112670583A (en) | Non-aqueous electrolyte composition for silicon-carbon negative electrode and application thereof | |
| CN115411360B (en) | Electrolyte of non-negative lithium metal battery and non-negative lithium metal battery |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| TA01 | Transfer of patent application right |
Effective date of registration: 20230412 Address after: 805, Building 9, No. 2, Jinlong Avenue, Baolong Community, Baolong Street, Longgang District, Shenzhen City, Guangdong Province, 518100 Applicant after: Shenzhen Huachi New Energy Technology Co.,Ltd. Address before: 434400 No. 17, Shiping Road, Jinping Industrial Park, Shishou Economic Development Zone, Jingzhou City, Hubei Province (independent application) Applicant before: Hubei Huachi New Energy Materials Co.,Ltd. |
|
| TA01 | Transfer of patent application right | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |