CN110518287B - Sodium ion electrolyte, secondary battery, preparation method and application - Google Patents
Sodium ion electrolyte, secondary battery, preparation method and application Download PDFInfo
- Publication number
- CN110518287B CN110518287B CN201910594885.5A CN201910594885A CN110518287B CN 110518287 B CN110518287 B CN 110518287B CN 201910594885 A CN201910594885 A CN 201910594885A CN 110518287 B CN110518287 B CN 110518287B
- Authority
- CN
- China
- Prior art keywords
- electrolyte
- additive
- phosphate
- sodium
- sodium salt
- 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
Images
Classifications
-
- A—HUMAN NECESSITIES
- A62—LIFE-SAVING; FIRE-FIGHTING
- A62C—FIRE-FIGHTING
- A62C3/00—Fire prevention, containment or extinguishing specially adapted for particular objects or places
- A62C3/16—Fire prevention, containment or extinguishing specially adapted for particular objects or places in electrical installations, e.g. cableways
-
- 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
-
- 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
- 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
-
- 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
- H01M2300/00—Electrolytes
- H01M2300/0017—Non-aqueous electrolytes
- H01M2300/0025—Organic electrolyte
- H01M2300/0028—Organic electrolyte characterised by the solvent
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- General Chemical & Material Sciences (AREA)
- Electrochemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Materials Engineering (AREA)
- Health & Medical Sciences (AREA)
- Public Health (AREA)
- Business, Economics & Management (AREA)
- Emergency Management (AREA)
- Secondary Cells (AREA)
Abstract
The invention discloses a sodium ion electrolyte, a secondary battery, a preparation method and application. The electrolyte comprises a basic electrolyte and an additive, wherein the basic electrolyte comprises a sodium salt and a flame-retardant solvent; the flame retardant solvent comprises a phosphate ester and a fluoroether; the additive comprises a fluorine-containing additive; the concentration of the sodium salt relative to the basic electrolyte is 1-2 mol/L; the concentration of the sodium salt relative to the phosphate is 1.5-3 mol/L; the volume ratio of the phosphate to the fluoroether is 1: 1-2: 1; the additive accounts for more than 0 and less than or equal to 5 wt% of the base electrolyte in percentage by mass. The sodium ion battery prepared by the electrolyte has good thermal stability, can form a stable SEI film to prevent the electrode and the electrolyte from reacting, has charge and discharge performance equivalent to that of the electrolyte taking carbonate as a solvent, and is low in manufacturing cost.
Description
Technical Field
The invention relates to a sodium ion electrolyte, a secondary battery, a preparation method and application.
Background
In recent years, sodium resources are abundant, cost is low, and the sodium can be applied to large-scale energy storage in the future, so that the sodium is a new hot spot of battery research at present. With the application of batteries in mobile phones, computers, electric vehicles and large-scale energy storage, the safety problem of battery systems becomes a key point of attention in the industry. Therefore, the safety of the sodium ion electrolyte has also received considerable attention from researchers.
The thermal stability of the electrolyte system and the non-flammability of the electrolyte solvent are major factors affecting the safety of the battery. Therefore, in order to improve the safety of the battery, it is most effective to develop a highly safe electrolyte system. For example, the onset of thermal runaway of a battery is due to the decomposition of an SEI film, thereby initiating reactions between an electrode material and an electrolyte and reactions between the electrode material and a binder, which are associated with the electrolyte. The thermal stability and non-flammability of the electrolyte are mainly determined by the composition of the solvent, salt and additive in the electrolyte, i.e. a high-safety electrolyte system can be designed from three directions of the selection of sodium salt, the selection of solvent system and the use of additive.
At present, the conventional solvent of the electrolyte in the field is a carbonate solvent, phosphorus-containing flame retardants, nitrogen-containing flame retardants and composite flame retardants are usually added to realize the non-flammability, but the electrolyte needs a very high concentration of flame retardants to realize the non-flammability. However, the high concentration of the flame retardant causes various problems such as phase separation of the electrolyte itself and loss of battery performance, and even though the above problems can be solved by using the high concentration of the salt, the high concentration of the salt is not only costly but also has a high viscosity of the electrolyte, which results in a problem that the flame retardant performance and the electrochemical performance cannot be simultaneously achieved, and thus, the practical application is difficult. In an electrolyte with carbonate (PC) as solvent, the thermal stability of the sodium salt is: NaClO4>NaPF6>NaTFSI, but different salts have different thermal behavior in different solvents.
Chinese patent CN103827416A proposes an electrolyte for use in a lithium ion battery, in which carbonate is used as a solvent, and a phosphazene compound, a fluorinated solvent, and an organic phosphate or an organic bony acid ester are used as a flame retardant cosolvent or an additive. But the discharge capacity of the electrolyte is not ideal and the cycle performance of the battery is poor.
Chinese patent CN2017104877213 proposes an electrolyte using LiBOB as a lithium salt and lactone and fluorinated ether as solvents for use in a lithium ion battery. However, the lactone is also a flammable solvent, and has poor thermal stability in the use process and potential safety hazards.
Therefore, in the prior art, a large amount of flame retardant is added to overcome the defect of flammability of the carbonate electrolyte, but the electrochemical performance is reduced, and if the problem that the nonflammability and the electrochemical performance cannot be considered is solved by increasing the salt concentration, the viscosity of the electrolyte is high; therefore, there is a need in the art to find an electrolyte solution that can overcome the above-mentioned difficulties, has good thermal stability, is not easily decomposed by a surface SEI film, and can prevent a reaction between an electrode and the electrolyte solution.
Disclosure of Invention
The invention provides a sodium ion electrolyte, a secondary battery, a preparation method and application thereof, and aims to solve the technical problems that in the prior art, an electrolyte solution with carbonate as a solvent has poor thermal stability, an SEI film is easy to decompose, a reaction can occur between an electrode and the electrolyte solution, and the electrochemical performance is reduced due to the addition of a large amount of flame retardant. The sodium ion battery prepared by the electrolyte has good thermal stability, can form a stable SEI film to prevent the electrode and the electrolyte from reacting, has charge and discharge performance equivalent to that of the electrolyte taking carbonate as a solvent, and has low manufacturing cost.
The inventor finds that the electrolyte with ideal electrochemical performance is prepared by adopting phosphate and fluoroether as flame-retardant solvents and adopting fluorine-containing additives under the condition of lower salt concentration, the electrochemical property is equivalent to that of carbonate electrolyte, and the electrolyte is not flammable; meanwhile, a stable SEI film can be formed to prevent chemical reaction between the electrode and the electrolyte, and the electrolyte has thermal stability. The electrolyte has both non-flammable performance and thermal stability, and is a high-safety electrolyte.
The invention solves the technical problems through the following technical scheme.
The invention provides an electrolyte, which comprises a basic electrolyte and an additive, wherein the basic electrolyte comprises a sodium salt and a flame-retardant solvent;
the flame retardant solvent comprises a phosphate ester and a fluoroether; the additive comprises a fluorine-containing additive; the concentration of the sodium salt relative to the basic electrolyte is 1-2 mol/L; the concentration of the sodium salt relative to the phosphate is 1.5-3 mol/L; the volume ratio of the phosphate to the fluoroether is 1: 1-2: 1; the additive accounts for more than 0 and less than or equal to 5 wt% of the base electrolyte in percentage by mass.
In the present invention, the sodium salt may be conventional in the art, and is preferably sodium hexafluorophosphate and/or sodium perchlorate.
In the present invention, the phosphate is preferably one or more of trimethyl phosphate, triethyl phosphate, tricresyl phosphate, triphenyl phosphate, dimethyl methyl phosphate, and diethyl ethyl phosphate.
In the present invention, the trimethyl phosphate is preferably anhydrous trimethyl phosphate.
In the present invention, the fluoroether is preferably one or more of 1,1,2, 2-tetrafluoroethyl-2, 2,3, 3-tetrafluoropropyl ether, 1,2, 2-tetrafluoroethyl-2, 2, 2-trifluoroethyl ether and 2H-perfluoro (5-methyl-3, 6-dioxanonane).
In the present invention, the fluorine-containing additive is preferably fluoroethylene carbonate. In the present invention, the concentration of the sodium salt relative to the phosphate is preferably 2.25 mol/L.
In the present invention, the concentration of the sodium salt with respect to the base electrolyte is preferably 1.5 mol/L.
In the present invention, the volume ratio of the phosphate ester to the fluoroether is preferably 2: 1.
In the present invention, the content of the additive is preferably 2 wt% based on the mass of the base electrolyte.
In a preferred embodiment of the present invention, said electrolyte is composed of said sodium salt, said phosphate ester, said fluoroether and said additive.
The invention also provides a preparation method of the electrolyte, which comprises the following steps: and uniformly mixing the basic electrolyte and the additive.
In the present invention, preferably, the mixing is performed under an inert atmosphere. For example, the mixing may be performed in a glove box.
Wherein the inert atmosphere is preferably argon.
The invention also provides an application of the electrolyte in a secondary battery.
In the present invention, the secondary battery may be a sodium secondary battery.
The invention also provides a secondary battery, and the electrolyte of the secondary battery is the electrolyte.
In the present invention, the positive electrode material of the secondary battery may be conventional in the art, and is preferably a layered metal oxide, more preferably NaNi1/3Fe1/3Mn1/3O2(NFM)。
In the present invention, the negative electrode material of the secondary battery may be conventional in the art, and is preferably a carbon-based material, and more preferably Hard Carbon (HC).
On the basis of the common knowledge in the field, the above preferred conditions can be combined randomly to obtain the preferred embodiments of the invention.
The reagents and starting materials used in the present invention are commercially available.
The positive progress effects of the invention are as follows:
the electrolyte disclosed by the invention has thermal stability and non-flammability, overcomes the defect that the flame retardant property and the electrochemical property of the electrolyte cannot be considered simultaneously due to the fact that a large amount of flame retardant is used under the condition that low-concentration salt is used, and has charge and discharge properties equivalent to those of the electrolyte taking carbonate as a solvent; a stable SEI film can be formed to prevent the reaction between the electrode and the electrolyte, and the electrolyte has good thermal stability and high safety; the sodium ion battery prepared by the electrolyte has high safety, rich sodium resources and low manufacturing cost in the large-scale industrial production process, and is suitable for industrial production.
Drawings
FIG. 1 is a comparative graph showing flammability tests of electrolytes of example 1 and comparative example 1 of the present invention.
Fig. 2 is a graph of the cycling performance of NFM/Na cells using the electrolytes of example 1, example 2 and comparative example 1 of the present invention.
Fig. 3 is a first turn charge and discharge curve for NFM/Na batteries using electrolytes of example 1, example 2 and comparative example 1 of the present invention.
Fig. 4 is a graph of the cycling performance of NFM/Na cells using the electrolytes of example 3, example 4, comparative example 3, and comparative example 4 of the present invention.
FIG. 5 is a first turn charge/discharge curve for HC/Na cells using electrolytes of example 1 and comparative example 6 of the present invention.
FIG. 6 is a first turn charge/discharge curve for HC/Na cells using electrolytes of example 5 and comparative example 5 of the present invention.
Detailed Description
The invention is further illustrated by the following examples, which are not intended to limit the scope of the invention. The experimental methods without specifying specific conditions in the following examples were selected according to the conventional methods and conditions, or according to the commercial instructions.
In the following examples and comparative examples, the method for preparing the electrolyte includes the step of uniformly mixing the base electrolyte and the additive. All mixing was performed in a glove box filled with argon.
Examples 1 to 6 and comparative examples 1 to 7
The components of the electrolytes prepared in examples 1 to 6 and comparative examples 1 to 7 are shown in table 1, and the contents of the components are shown in table 2.
TABLE 1 Components of the electrolyte
TABLE 2 contents of the respective components in the electrolyte
Among them, in comparative example 1, conventional carbonate-based solvents were used instead of the phosphate esters and fluoroethers used in the present application, and electrochemical properties and flame resistance thereof were sought; the electrochemical properties without the use of the additive fluoroethylene carbonate were explored in comparative examples 2-7.
Effect example 1
The evaluation method of the battery performance is carried out according to the industry standard.
The secondary battery adopting the electrolyte disclosed by the invention is used for carrying out charge and discharge performance tests. The cell was first charged and discharged at a low current density of 0.1C, and then subjected to a cycling test at a current density of 1C.
As can be seen from fig. 1, the electrolyte prepared in example 1 of the present invention has non-flammable characteristics under the condition of a fire source for a sufficient time. Under the same conditions, the carbonate electrolyte prepared in comparative example 1 can be continuously combusted after leaving the fire source until the electrolyte is completely combusted. Therefore, the electrolyte of the present invention has significant advantages in improving the safety of the battery.
As can be seen from FIG. 2, the electrolyte of the invention is applied to NaNi of a sodium ion battery1/3Fe1/3Mn1/3O2In the (NFM) layered material, the discharge capacity of the electrolyte battery of the invention is higher than that of the carbonate-based conventional electrolyte, after 100 cycles, the capacity retention rates of example 1 and example 2 are 79% and 83%, respectively, and the capacity retention rate of comparative example 1 is 81%, which indicates that the electrolyte of the invention has substantially equivalent capacity retention rate to that of comparative example 1, and the battery of example 2 has better cycle stability.
The results of example 1 and example 2 in FIG. 3 show that the inventionApplication of electrolyte to NaNi of sodium ion battery1/3Fe1/3Mn1/3O2(NFM) layered material, the solvent of the electrolyte is composed of trimethyl phosphate and 1,1,2, 2-tetrafluoroethyl-2, 2,3, 3-tetrafluoropropyl ether, and the volume ratio of trimethyl phosphate to 1,1,2, 2-tetrafluoroethyl-2, 2,3, 3-tetrafluoropropyl ether is 2:1 to 1:1, the discharge specific capacity is better; the first charge-discharge capacity of the electrolyte prepared in example 1 was: 130.3mAh/g (charging)/127.8 mAh/g (discharging), and the first coulombic efficiency is 98.1%; the first charge-discharge capacity of the electrolyte prepared in the example 2 is 135.5mAh/g (charge)/129.9 mAh/g (discharge), and the first efficiency coulomb is 95.87%; the first charge-discharge capacity of the conventional carbonate electrolyte prepared in comparative example 1 was: 133.5mAh/g (charge)/122.5 mAh/g (discharge), and the first coulombic efficiency is 91.72%. Therefore, the first efficiency of the electrolyte prepared by the invention is equivalent to that of the traditional carbonate electrolyte, and the battery has good cycling stability. Therefore, the electrolyte can improve the safety of the battery and simultaneously shows good electrochemical performance.
As can be seen from FIG. 4, the electrolytes with different salt concentrations prepared in example 3, example 4, comparative example 3 and comparative example 4 were applied to NaNi of a sodium ion battery1/3Fe1/3Mn1/3O2(NFM) cycling performance in layered positive electrode materials. As can be seen from the figure, when the volume ratio of trimethyl phosphate to 1,1,2, 2-tetrafluoroethyl-2, 2,3, 3-tetrafluoropropyl ether is 2:1, the fluoroethylene carbonate (FEC) additive is added to effectively improve the stability of the electrolyte and improve the capacity retention rate of the battery, particularly under the condition of low sodium salt concentration. The reason why the concentration of sodium hexafluorophosphate was 1mol/L with respect to the concentration of the base electrolyte in comparative example 3 is that the salt concentration was low, the solvent was continuously decomposed, a stable interface could not be formed on the Na negative electrode side, a severe dendrite phenomenon occurred, and finally the dendrite penetrated the separator, resulting in a rapid decrease in discharge capacity. The capacity retention rate is significantly improved after the fluoroethylene carbonate is added in example 3. In comparative example 4, the sodium hexafluorophosphate was present in a concentration of 2mol/L relative to the base electrolyte, and the conductivity was low, although the decomposition of the solvent did not occur continuouslyHowever, when the electrolyte of comparative example 4 is applied to a Hard Carbon (HC) negative electrode material of a sodium ion battery, the first turn of coulombic efficiency is significantly reduced compared with that of example 4 (see effect example 2 for specific data), and comprehensively considering that the electrolyte of comparative example 4 has poor electrochemical performance.
Fig. 5 is a first round of charge and discharge images of the electrolytes of example 1 and comparative example 6 applied to a Hard Carbon (HC) anode material of a sodium ion battery. The battery of comparative example 6 showed a discharge plateau around 0.25V in the first discharge graph, because a stable SEI film could not be formed on the surface of the negative electrode and the solvent molecules of the electrolyte were continuously decomposed on the surface of the electrode sheet. In contrast, after the FEC additive is added, it is decomposed at a potential of about 0.7V as an effective negative electrode film-forming agent, thereby inhibiting the reduction of solvent molecules of the electrolyte.
Fig. 6 is a first round of charge and discharge images of the electrolytes of example 5 and comparative example 5 applied to a Hard Carbon (HC) anode material of a sodium ion battery. As can be seen from fig. 6, the application of sodium perchlorate and sodium hexafluorophosphate as sodium salts in the sodium ion battery electrolyte has the same performance, that is, when the FEC additive is added, a discharge platform appears in the first discharge loop at about 0.25V, and the platform disappears after the FEC additive is added, that is, the FEC additive preferentially forms a film on the electrode surface, so that the decomposition of solvent molecules can be effectively inhibited.
Effect example 2
The charge and discharge performance tests of the secondary batteries using the electrolytes of examples 1 to 6 of the present invention and comparative examples 1 to 7 are shown in table 1. The experimental results show that when FEC is not added to the electrolyte, the first-turn coulombic efficiency of the Hard Carbon (HC)/Na negative electrode is significantly reduced, the electrochemical performance is relatively poor, and it is not worth further performing a targeted effect test, so that the electrochemical parameters of the electrolyte in the Hard Carbon (HC)/Na negative electrode in all comparative examples are not tested, and "-" in table 3 represents untested data.
TABLE 3
Wherein, the electrolyte of comparative example 4 is not added with additives compared with the electrolyte of example 4, and when the electrolyte of comparative example 4 is applied to a Hard Carbon (HC) negative electrode material of a sodium ion battery, the first turn coulombic efficiency is significantly reduced and the electrochemical performance is poor compared with example 4.
The electrolyte of comparative example 6 is applied to a Hard Carbon (HC) negative electrode material of a sodium ion battery, although the charge and discharge capacity of the first circle is high, a discharge platform appears around 0.25V (as shown in fig. 5), which is caused by the continuous decomposition of solvent molecules of the electrolyte on the surface of a pole piece, and further causes poor cycle performance.
While specific embodiments of the invention have been described above, it will be appreciated by those skilled in the art that this is by way of example only, and that the scope of the invention is defined by the appended claims. Various changes and modifications to these embodiments may be made by those skilled in the art without departing from the spirit and scope of the invention, and these changes and modifications are within the scope of the invention.
Claims (7)
1. The electrolyte of the sodium ion secondary battery is characterized in that the positive electrode material of the sodium ion secondary battery is NaNi1/3Fe1/3Mn1/3O2The negative electrode material is Na, which comprises one of the following formulas:
the formula I is as follows:
a base electrolyte and an additive, wherein the base electrolyte comprises a sodium salt and a flame-retardant solvent; the flame retardant solvent comprises a phosphate ester and a fluoroether; the additive comprises a fluorine-containing additive; the concentration of the sodium salt relative to the base electrolyte is 1.5 mol/L; the concentration of the sodium salt relative to the phosphate is 3 mol/L; the volume ratio of the phosphate to the fluoroether is 1: 1; the content of the additive accounts for 2 wt% of the mass percent of the basic electrolyte;
the sodium salt is sodium hexafluorophosphate;
the phosphate is anhydrous trimethyl phosphate;
the fluoroether is 1,1,2, 2-tetrafluoroethyl-2, 2,3, 3-tetrafluoropropyl ether;
the fluorine-containing additive is fluoroethylene carbonate;
the first-circle discharge capacity of the sodium ion secondary battery is 127.8mAh g-1；
And a second formula:
a base electrolyte and an additive, wherein the base electrolyte comprises a sodium salt and a flame-retardant solvent; the flame retardant solvent comprises a phosphate ester and a fluoroether; the additive comprises a fluorine-containing additive; the concentration of the sodium salt relative to the base electrolyte is 1.5 mol/L; the concentration of the sodium salt relative to the phosphate is 2.25 mol/L; the volume ratio of the phosphate to the fluoroether is 2: 1; the content of the additive accounts for 2 wt% of the mass percent of the basic electrolyte;
the sodium salt is sodium hexafluorophosphate;
the phosphate is anhydrous trimethyl phosphate;
the fluoroether is 1,1,2, 2-tetrafluoroethyl-2, 2,3, 3-tetrafluoropropyl ether;
the fluorine-containing additive is fluoroethylene carbonate;
the first-circle discharge capacity of the sodium ion secondary battery is 129.9mAh g-1；
And the formula III:
a base electrolyte and an additive, wherein the base electrolyte comprises a sodium salt and a flame-retardant solvent; the flame retardant solvent comprises a phosphate ester and a fluoroether; the additive comprises a fluorine-containing additive; the concentration of the sodium salt relative to the base electrolyte is 1 mol/L; the concentration of the sodium salt relative to the phosphate is 2.25 mol/L; the volume ratio of the phosphate to the fluoroether is 2: 1; the content of the additive accounts for 2 wt% of the mass percent of the basic electrolyte;
the sodium salt is sodium hexafluorophosphate;
the phosphate is anhydrous trimethyl phosphate;
the fluoroether is 1,1,2, 2-tetrafluoroethyl-2, 2,3, 3-tetrafluoropropyl ether;
the fluorine-containing additive is fluoroethylene carbonate;
the first-circle discharge capacity of the sodium ion secondary battery is 126.5mAh g-1；
The formula four:
a base electrolyte and an additive, wherein the base electrolyte comprises a sodium salt and a flame-retardant solvent; the flame retardant solvent comprises a phosphate ester and a fluoroether; the additive comprises a fluorine-containing additive; the concentration of the sodium salt relative to the base electrolyte is 2 mol/L; the concentration of the sodium salt relative to the phosphate is 3 mol/L; the volume ratio of the phosphate to the fluoroether is 2: 1; the content of the additive accounts for 2 wt% of the mass percent of the basic electrolyte;
the sodium salt is sodium hexafluorophosphate;
the phosphate is anhydrous trimethyl phosphate;
the fluoroether is 1,1,2, 2-tetrafluoroethyl-2, 2,3, 3-tetrafluoropropyl ether;
the fluorine-containing additive is fluoroethylene carbonate;
the first-circle discharge capacity of the sodium ion secondary battery is 127.6mAh g-1；
And a fifth formula:
a base electrolyte and an additive, wherein the base electrolyte comprises a sodium salt and a flame-retardant solvent; the flame retardant solvent comprises a phosphate ester and a fluoroether; the additive comprises a fluorine-containing additive; the concentration of the sodium salt relative to the base electrolyte is 1.5 mol/L; the concentration of the sodium salt relative to the phosphate is 2.25 mol/L; the volume ratio of the phosphate to the fluoroether is 2: 1; the content of the additive accounts for 2 wt% of the mass percent of the basic electrolyte;
the sodium salt is sodium perchlorate;
the phosphate is anhydrous trimethyl phosphate;
the fluoroether is 1,1,2, 2-tetrafluoroethyl-2, 2,3, 3-tetrafluoropropyl ether;
the fluorine-containing additive is fluoroethylene carbonate;
the sodium ionThe first-circle discharge capacity of the secondary battery is 126.5mAh g-1。
2. The electrolyte for sodium ion secondary batteries according to claim 1, characterized in that it consists of said sodium salt, said phosphate ester, said fluoroether and said additive.
3. A method for preparing the electrolyte of the sodium-ion secondary battery according to claim 1 or 2, comprising the steps of: and uniformly mixing the basic electrolyte and the additive.
4. The method of claim 3, wherein the mixing is performed under an inert atmosphere.
5. The method of claim 4, wherein the inert atmosphere is argon.
6. Use of the electrolyte of a sodium-ion secondary battery according to claim 1 or 2 in a sodium-ion secondary battery.
7. A sodium ion secondary battery characterized in that the electrolyte is the electrolyte of the sodium ion secondary battery according to claim 1 or 2.
Priority Applications (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910594885.5A CN110518287B (en) | 2019-07-03 | 2019-07-03 | Sodium ion electrolyte, secondary battery, preparation method and application |
| PCT/CN2019/113924 WO2020088436A1 (en) | 2018-10-29 | 2019-10-29 | Electrolyte, additive thereof, secondary cell, and application thereof |
| US17/286,821 US12107223B2 (en) | 2018-10-29 | 2019-10-29 | Electrolyte, additive thereof, secondary cell, and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910594885.5A CN110518287B (en) | 2019-07-03 | 2019-07-03 | Sodium ion electrolyte, secondary battery, preparation method and application |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN110518287A CN110518287A (en) | 2019-11-29 |
| CN110518287B true CN110518287B (en) | 2022-02-11 |
Family
ID=68623608
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201910594885.5A Active CN110518287B (en) | 2018-10-29 | 2019-07-03 | Sodium ion electrolyte, secondary battery, preparation method and application |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN110518287B (en) |
Families Citing this family (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US12107223B2 (en) | 2018-10-29 | 2024-10-01 | Shanghai Zijian Chemical Technology Co., Ltd | Electrolyte, additive thereof, secondary cell, and application thereof |
| CN111082140A (en) * | 2019-12-19 | 2020-04-28 | 东莞市坤乾新能源科技有限公司 | Novel sodium ion battery electrolyte and sodium battery |
| CN113113670A (en) * | 2021-04-09 | 2021-07-13 | 浙江大学山东工业技术研究院 | Non-combustible lithium metal battery electrolyte and preparation method thereof, lithium metal battery and preparation method thereof |
| CN114039095A (en) * | 2021-12-09 | 2022-02-11 | 河南省法恩莱特新能源科技有限公司 | Flame-retardant sodium-ion battery electrolyte |
| CN114464885A (en) * | 2022-02-16 | 2022-05-10 | 温州大学碳中和技术创新研究院 | Flame-retardant sodium-ion battery electrolyte and preparation method of safe sodium-ion battery |
| CN114566713B (en) * | 2022-03-08 | 2023-09-29 | 中国矿业大学 | Electrolyte, preparation method thereof and method for preparing sodium ion battery by using electrolyte |
| CN115347235B (en) * | 2022-07-25 | 2023-04-28 | 中南大学 | Sodium ion battery electrolyte and sodium ion battery with high multiplying power and stable circulation |
| CN118117147A (en) * | 2022-11-29 | 2024-05-31 | 深圳新宙邦科技股份有限公司 | High-safety long-circulation sodium ion battery |
| CN115663287B (en) * | 2022-12-13 | 2023-04-04 | 湖南法恩莱特新能源科技有限公司 | High-pressure-resistant flame-retardant sodium ion electrolyte, preparation method thereof and sodium ion battery |
| CN116093433A (en) * | 2023-02-10 | 2023-05-09 | 厦门海辰储能科技股份有限公司 | Battery, battery pack and electric equipment |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104900879A (en) * | 2015-06-01 | 2015-09-09 | 山东大学 | Flame retardant sodium-ion battery electrolytic solution and application thereof |
| CN105655631A (en) * | 2016-03-30 | 2016-06-08 | 武汉大学 | Incombustible sodium secondary battery, electrolyte thereof and application of incombustible sodium secondary battery |
| CN106920988A (en) * | 2017-04-01 | 2017-07-04 | 上海中聚佳华电池科技有限公司 | A kind of sodium-ion battery electrolyte, its preparation method and application |
| CN108183257A (en) * | 2017-12-26 | 2018-06-19 | 深圳先进技术研究院 | Organogel electrolyte, application, sodium base double ion organic solid-state battery and preparation method thereof |
| KR101911520B1 (en) * | 2017-08-25 | 2018-10-25 | 한국전기연구원 | Liquid Electrolytes For Na Secondary Batteries And Na Secondary Batteries Comprising The Same |
| CN109786840A (en) * | 2018-10-29 | 2019-05-21 | 上海紫剑化工科技有限公司 | High safety type organic electrolyte, secondary cell and preparation method and application |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102637894B (en) * | 2012-04-06 | 2014-11-05 | 宁德新能源科技有限公司 | Secondary battery with non-aqueous electrolyte |
| US10472571B2 (en) * | 2017-03-02 | 2019-11-12 | Battelle Memorial Institute | Low flammability electrolytes for stable operation of electrochemical devices |
| CN107171020A (en) * | 2017-06-13 | 2017-09-15 | 中国电子新能源（武汉）研究院有限责任公司 | Sodium-ion battery nonaqueous electrolytic solution and sodium-ion battery |
-
2019
- 2019-07-03 CN CN201910594885.5A patent/CN110518287B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104900879A (en) * | 2015-06-01 | 2015-09-09 | 山东大学 | Flame retardant sodium-ion battery electrolytic solution and application thereof |
| CN105655631A (en) * | 2016-03-30 | 2016-06-08 | 武汉大学 | Incombustible sodium secondary battery, electrolyte thereof and application of incombustible sodium secondary battery |
| CN106920988A (en) * | 2017-04-01 | 2017-07-04 | 上海中聚佳华电池科技有限公司 | A kind of sodium-ion battery electrolyte, its preparation method and application |
| KR101911520B1 (en) * | 2017-08-25 | 2018-10-25 | 한국전기연구원 | Liquid Electrolytes For Na Secondary Batteries And Na Secondary Batteries Comprising The Same |
| CN108183257A (en) * | 2017-12-26 | 2018-06-19 | 深圳先进技术研究院 | Organogel electrolyte, application, sodium base double ion organic solid-state battery and preparation method thereof |
| CN109786840A (en) * | 2018-10-29 | 2019-05-21 | 上海紫剑化工科技有限公司 | High safety type organic electrolyte, secondary cell and preparation method and application |
Also Published As
| Publication number | Publication date |
|---|---|
| CN110518287A (en) | 2019-11-29 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN110518287B (en) | Sodium ion electrolyte, secondary battery, preparation method and application | |
| WO2020088436A1 (en) | Electrolyte, additive thereof, secondary cell, and application thereof | |
| CN102522590B (en) | Non-aqueous organic electrolyte, lithium ion secondary battery containing non-aqueous organic electrolyte, preparation method of lithium ion secondary battery and terminal communication equipment | |
| CN102306838B (en) | A kind of non-aqueous electrolyte for lithium ion cell and the battery made thereof | |
| CN102569885B (en) | Lithium ion battery nonaqueous electrolytic solution and lithium rechargeable battery | |
| CN111129586A (en) | High-voltage lithium cobalt oxide lithium ion battery non-aqueous electrolyte and lithium ion battery | |
| CN106558732B (en) | A kind of lithium-ion battery electrolytes and lithium ion battery | |
| CN102306833A (en) | Flame retardant type non-aqueous electrolyte solution and battery thereof | |
| CN109786840B (en) | High-safety organic electrolyte, secondary battery, preparation method and application | |
| CN108232296B (en) | Electrolyte solution and lithium secondary battery | |
| CN111129598A (en) | High-voltage lithium ion battery non-aqueous electrolyte and lithium ion battery thereof | |
| WO2023207369A1 (en) | Lithium-ion battery | |
| CN114300750A (en) | Lithium ion battery electrolyte and lithium ion battery | |
| CN115799643A (en) | Nonaqueous electrolyte solution, lithium ion battery, battery module, battery pack, and electric device | |
| CN115799644A (en) | Low-concentration flame-retardant electrolyte and secondary battery | |
| CN111146500A (en) | Fast-charging type lithium ion battery non-aqueous electrolyte and lithium ion battery containing electrolyte | |
| CN104466251B (en) | A kind of electrolyte and the lithium ion battery using the electrolyte | |
| CN116936810B (en) | Positive pole piece of sodium ion battery and sodium ion battery | |
| CN115763971A (en) | High-voltage lithium cobalt oxide lithium ion battery non-aqueous electrolyte and lithium ion battery | |
| CN117691190A (en) | Electrolyte for lithium-rich manganese-based positive electrode high-voltage lithium ion battery and lithium ion battery | |
| CN116344939A (en) | Nonaqueous electrolyte and sodium ion battery | |
| Chang et al. | The guarantee of large-scale energy storage: Non-flammable organic liquid electrolytes for high-safety sodium ion batteries | |
| CN115882070A (en) | Electrolyte and lithium metal battery containing same | |
| CN116845360B (en) | sodium ion battery | |
| CN117117329B (en) | Sodium ion battery electrolyte and sodium ion 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 | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| TR01 | Transfer of patent right | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20230105 Address after: 312366 2nd floor, building B, kechuangyuan, 398 mahuan Road, Binhai New Town, Shaoxing City, Zhejiang Province Patentee after: Zhejiang sodium innovation energy Co.,Ltd. Address before: Room 6108, 6 storeys, Building 5, No. 951 Jianchuan Road, Minhang District, Shanghai, 200240 Patentee before: SHANGHAI ZIJIAN CHEMICAL TECHNOLOGY Co.,Ltd. Patentee before: SHENZHEN CAPCHEM TECHNOLOGY Co.,Ltd. |