CN114976249A - Electrolyte and sodium ion battery - Google Patents

Electrolyte and sodium ion battery Download PDF

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Publication number
CN114976249A
CN114976249A CN202210738856.3A CN202210738856A CN114976249A CN 114976249 A CN114976249 A CN 114976249A CN 202210738856 A CN202210738856 A CN 202210738856A CN 114976249 A CN114976249 A CN 114976249A
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electrolyte
carbonate
sodium
functional additive
organic solvent
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刘鹏
徐雄文
王志斌
黄玉希
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Hunan Nafang New Energy Technology Co ltd
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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
    • 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
    • H01M10/42—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
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Materials Engineering (AREA)
  • Physics & Mathematics (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • General Physics & Mathematics (AREA)
  • Inorganic Chemistry (AREA)
  • Secondary Cells (AREA)

Abstract

The invention belongs to the technical field of secondary batteries, and particularly relates to an electrolyte and a sodium ion battery, which comprise a conductive sodium salt, a non-aqueous organic solvent and a functional additive, wherein the functional additive comprises one or more of fluoroethylene carbonate, ethylene sulfate, isatoic anhydride and tris (trimethylsilane) borate. The electrolyte adopts the combination of several functional additives, can generate synergistic action, can form a stable and compact interfacial film on a positive electrode and a negative electrode, can partially neutralize the alkalinity on the surface of a positive electrode material, inhibit side reaction with the electrolyte, improve the charge transfer capacity of an electrode, and combines several low-resistance additives, so that the formed interfacial film has small impedance, and the polarization of a battery is reduced, thereby having both low temperature and rate performance while having excellent circulation.

Description

Electrolyte and sodium ion battery
Technical Field
The invention belongs to the technical field of secondary batteries, and particularly relates to an electrolyte and a sodium ion battery.
Background
With the gradual scarcity of traditional fossil energy and the increasingly serious environmental problems, the development of new renewable energy has become a necessary trend. Lithium ion batteries have been widely used in electric vehicles, notebook computers, energy storage, etc. because of their advantages of high energy density, long cycle life, environmental friendliness, etc., but lithium has a limited resource reserve, is unevenly distributed on the earth, and will be exhausted in the future. Sodium is one of elements with abundant reserves on the earth, has a working principle similar to that of a lithium ion battery, has the advantages of low cost, good safety, capability of long-term large-scale storage and the like, is more and more concerned by research and development personnel, and is expected to be widely applied to the field of energy storage instead of the lithium ion battery.
However, the positive electrode material of the sodium ion battery has strong alkalinity and is easy to react with the electrolyte, and particularly under high voltage, the side reaction is more serious, and gas is generated, so that the problems of battery internal pressure increase, battery deformation, performance attenuation and the like are caused, and therefore, the problem of gas generation of the battery is urgently solved.
Disclosure of Invention
The invention aims to: aiming at the defects of the prior art, the electrolyte is provided, can neutralize the alkalinity of the surface of the anode material, improves the compactness and stability of the SEI film, does not generate side reaction under high voltage, does not generate gas and does not deform.
In order to achieve the purpose, the invention adopts the following technical scheme:
an electrolyte comprising a conductive sodium salt, a non-aqueous organic solvent, and a functional additive comprising one or more of fluoroethylene carbonate, vinyl sulfate, isatoic anhydride, tris (trimethylsilane) borate.
Preferably, the functional additive accounts for 1-10% of the total mass of the electrolyte.
Preferably, the conductive sodium salt comprises one or more of sodium hexafluorophosphate, sodium perchlorate, sodium difluorophosphate and sodium bisoxalato.
Preferably, the conductive sodium salt accounts for 12-18% of the total weight of the electrolyte.
Preferably, the non-aqueous organic solvent comprises one or a mixture of cyclic carbonate, chain carbonate, ethyl propionate and propyl propionate.
Preferably, the mass ratio of the cyclic carbonate to the chain carbonate is 1:1 to 4.
Preferably, the cyclic carbonate comprises one or a mixture of ethylene carbonate and propylene carbonate, and the chain carbonate comprises one or a mixture of dimethyl carbonate, diethyl carbonate and ethyl methyl carbonate.
Preferably, the mass of the non-aqueous organic solvent accounts for 70-85% of the total mass of the electrolyte.
Preferably, the functional additive is a mixture of fluoroethylene carbonate, vinyl sulfate, tris (trimethylsilane) borate and isatoic anhydride in a weight ratio of 2-8: 0.2-5: 0.1-5.
The invention aims to: aiming at the defects of the prior art, the sodium ion battery has the advantages of good high-voltage stability, good cycle performance and long service life.
In order to achieve the purpose, the invention adopts the following technical scheme:
a sodium ion battery comprises the electrolyte.
Compared with the prior art, the invention has the beneficial effects that:
the functional additives in the invention comprise fluoroethylene carbonate, ethylene sulfate, isatoic anhydride and tris (trimethylsilane) borate. The fluoroethylene carbonate forms a stable and compact SEI film on the negative electrode, so that the wettability of the electrolyte is improved, and the impedance of the battery is reduced; the isatoic anhydride can neutralize the alkalinity of the surface of the anode material and can form a film on the anode, and the fluoroanhydride can generate NaF, thereby improving the conductivity, reducing the internal resistance, inhibiting the generation of cracks in the anode material particles in the circulation process and improving the circulation; the vinyl sulfate forms a low-impedance SEI film on the negative electrode, so that the impedance increase of the battery in circulation is reduced, and the low-temperature and rate performance is improved; the tris (trimethylsilane) borate forms a stable and compact CEI film on the anode, so that the dissolution of transition metal of the anode material is inhibited, the stability of the anode material is improved, the charge transfer capacity of the electrode can be improved, and the circulation is improved. The isatoic anhydride comprises one or more of isatoic anhydride, 5-fluoroisatoic anhydride and 6-fluoroisatoic anhydride.
The invention adopts the combination of several additives, can generate synergistic action, can form a stable and compact interfacial film on the positive and negative electrodes, can partially neutralize the alkalinity on the surface of the positive electrode material, inhibit side reaction with electrolyte, improve the charge transfer capability of the electrode, and combines several low-resistance additives, the formed interfacial film has small impedance, and reduces the polarization of the battery, thereby having both low temperature and multiplying power performance while having excellent circulation.
Detailed Description
1. An electrolyte comprising a conductive sodium salt, a non-aqueous organic solvent and a functional additive comprising one or more of fluoroethylene carbonate, vinyl sulfate, isatoic anhydride, tris (trimethylsilane) borate.
The functional additives in the invention comprise fluoroethylene carbonate, ethylene sulfate, isatoic anhydride and tris (trimethylsilane) borate. The fluoroethylene carbonate forms a stable and compact SEI film on the negative electrode, so that the wettability of the electrolyte is improved, and the impedance of the battery is reduced; the isatoic anhydride can neutralize the alkalinity of the surface of the anode material and can form a film on the anode, and the fluoroanhydride can generate NaF, thereby improving the conductivity, reducing the internal resistance, inhibiting the generation of cracks in the anode material particles in the circulation process and improving the circulation; the vinyl sulfate forms a low-impedance SEI film on the negative electrode, so that the impedance increase of the battery in circulation is reduced, and the low-temperature and rate performance is improved; the tris (trimethylsilane) borate forms a stable and compact CEI film on the anode, so that the dissolution of transition metal of the anode material is inhibited, the stability of the anode material is improved, the charge transfer capacity of the electrode can be improved, and the circulation is improved. The isatoic anhydride comprises one or more of isatoic anhydride, 5-fluoroisatoic anhydride and 6-fluoroisatoic anhydride.
The invention adopts the combination of several additives, can generate synergistic action, can form a stable and compact interfacial film on the positive and negative electrodes, can partially neutralize the alkalinity on the surface of the positive electrode material, inhibit side reaction with electrolyte, improve the charge transfer capability of the electrode, and combines several low-resistance additives, the formed interfacial film has small impedance, and reduces the polarization of the battery, thereby having both low temperature and multiplying power performance while having excellent circulation.
Preferably, the functional additive accounts for 1-10% of the total mass of the electrolyte. The functional additive accounts for 2-10%, 4-8%, 4-7% and 4-6% of the total mass of the electrolyte, and specifically, the functional additive accounts for 1%, 2%, 3%, 4%, 5%, 6%, 7%, 8%, 9% and 10% of the total mass of the electrolyte.
Preferably, the conductive sodium salt comprises one or more of sodium hexafluorophosphate, sodium perchlorate, sodium difluorophosphate and sodium bisoxalato.
Preferably, the conductive sodium salt accounts for 12-18% of the total weight of the electrolyte. The conductive sodium salt accounts for 13-18%, 13-17% and 14-16% of the total weight of the electrolyte, and specifically, the conductive sodium salt accounts for 12%, 14%, 16% and 18% of the total weight of the electrolyte.
Preferably, the non-aqueous organic solvent comprises one or a mixture of several of cyclic carbonate, chain carbonate, ethyl propionate and propyl propionate.
Preferably, the mass ratio of the cyclic carbonate to the chain carbonate is 1:1 to 4. The mass ratio of the cyclic carbonate to the chain carbonate is 1:1, 1:2, 1:3, 1: 4.
Preferably, the cyclic carbonate comprises one or a mixture of ethylene carbonate and propylene carbonate, and the chain carbonate comprises one or a mixture of dimethyl carbonate, diethyl carbonate and ethyl methyl carbonate.
Preferably, the mass of the non-aqueous organic solvent accounts for 70-85% of the total mass of the electrolyte. The mass of the nonaqueous organic solvent accounts for 70%, 74%, 77%, 79%, 82%, 85% of the total mass of the electrolyte.
Preferably, the functional additive is a mixture of fluoroethylene carbonate, vinyl sulfate, tris (trimethylsilane) borate and isatoic anhydride in a weight ratio of 2-8: 0.2-5: 0.1-5. Preferably, the weight part ratio of the fluoroethylene carbonate, the vinyl sulfate, the tris (trimethylsilane) borate to the isatoic anhydride is 2-8: 0.2-5: 0.3-5, 2-8: 0.2-5: 0.1-4, 2-8: 0.2-5: 0.1-3, 2-8: 0.2-5: 0.1-2, 2-8: 0.2-3: 0.1-2.
2. The sodium ion battery has the advantages of good high-voltage stability, good cycle performance and long service life.
A sodium ion battery comprises the electrolyte.
The present invention will be described in further detail with reference to specific embodiments, but the embodiments of the present invention are not limited thereto.
Example 1
1. An electrolyte comprising a conductive sodium salt and a non-aqueous organic solvent and functional additives including fluoroethylene carbonate, vinyl sulfate, tris (trimethylsilane) borate and isatoic anhydride.
The preparation method of the electrolyte comprises the following steps: mixing NaPF 6 (sodium hexafluorophosphate), a mixed organic solvent (PC: DEC: EMC ═ 3:2:5), FEC (fluoroethylene carbonate), DTD (vinyl sulfate), TMSB (tris (trimethylsilane) borate), and isatoic anhydride were mixed, and the mixture was stirred with a vacuum stirrer until stable and uniform to obtain an electrolytic solution. Wherein, NaPF 6 The mass of the mixed organic solvent, fluoroethylene carbonate, vinyl sulfate, tris (trimethylsilane) borate and isatoic anhydride respectively accounts for 14%, 79%, 5%, 1%, 0.5% and 0.5% of the total mass of the electrolyte.
The electrolyte is used in a sodium-ion battery, and the sodium-ion battery further comprises a positive plate, a negative plate and a diaphragm which is arranged between the positive plate and the negative plate.
The preparation method of the sodium ion battery comprises the following steps:
1) preparing a positive plate: the positive electrode material Na [ Ni ] 1/3 Mn 1/3 Fe 1/3 ]O 2 The adhesive PVDF and the conductive agent Super-P are dispersed in NMP organic solvent according to the mass ratio of 96:2:2, and are stirred to be stable and uniform under the action of a vacuum stirrer, and are uniformly coated on an aluminum foil with the thickness of 12 mu m. And (3) airing the aluminum foil at room temperature, transferring the aluminum foil to a blast oven at 120 ℃ for drying for 1h, and then performing cold pressing and die cutting to prepare the positive plate.
2) Preparing a negative plate: according to the mass ratio of 97:2:1, spherical hard carbon, a binder PVDF and a conductive agent Super-P are mixed together and dispersed in an NMP organic solvent, so that the aluminum foil with the thickness of 12 mu m is uniformly coated. And (3) airing the aluminum foil at room temperature, transferring the aluminum foil to a blast oven at 120 ℃ for drying for 1h, and then performing cold pressing and die cutting to prepare the negative plate.
3) And (3) obtaining a naked battery core by laminating the positive plate, the negative plate and the polypropylene diaphragm, filling the battery core into an aluminum-plastic film packaging shell, injecting the electrolyte, sequentially sealing, and performing standing, hot-cold pressing, formation, capacity grading and other processes to obtain the sodium ion battery.
Example 2
The difference from example 1 is the arrangement of the electrolyte additive. In this example, the mass fraction of the functional additive isatoic anhydride was adjusted to 0.3%, and the mass fraction of the organic solvent was adjusted to 79.2%.
The rest is the same as the embodiment 1, and the description is omitted here.
Example 3
The difference from example 1 is the arrangement of the electrolyte additive. In this example, the mass fraction of the functional additive isatoic anhydride was adjusted to 1%, and the mass fraction of the organic solvent was adjusted to 78.5%.
The rest is the same as embodiment 1, and the description is omitted here.
Example 4
The difference from example 1 is the arrangement of the electrolyte additive. In this example, the mass fraction of the functional additive isatoic anhydride was adjusted to 2%, and the mass fraction of the organic solvent was adjusted to 77.5%.
The rest is the same as embodiment 1, and the description is omitted here.
Example 5
The difference from example 1 is the arrangement of the electrolyte additive. In this example, the mass fraction of the functional additive isatoic anhydride was adjusted to 5%, and the mass fraction of the organic solvent was adjusted to 74.5%.
The rest is the same as embodiment 1, and the description is omitted here.
Example 6
The difference from example 1 is the arrangement of the electrolyte additive. In this example, the mass fraction of the functional additive isatoic anhydride was adjusted to 5-fluoroisatoic anhydride.
The rest is the same as embodiment 1, and the description is omitted here.
Example 7
The difference from example 1 is the arrangement of the electrolyte additive. In this example, the mass fraction of the functional additive isatoic anhydride was adjusted to 6-fluoroisatoic anhydride.
The rest is the same as embodiment 1, and the description is omitted here.
Comparative example 1
The difference from example 1 is the arrangement of the electrolyte additive. The comparative example does not use fluoroethylene carbonate (FEC) as a functional additive and the mass fraction of the organic solvent is adjusted to 84%.
The rest is the same as embodiment 1, and the description is omitted here.
Comparative example 2
The difference from example 1 is the arrangement of the electrolyte additive. This comparative example does not use a functional additive of vinyl sulfate (DTD), and the mass fraction of the organic solvent is adjusted to 80%.
The rest is the same as embodiment 1, and the description is omitted here.
Comparative example 3
The difference from example 1 is the provision of the electrolyte additive. This comparative example does not use the functional additive TMSB and the mass fraction of the organic solvent is adjusted to 79.5%.
The rest is the same as embodiment 1, and the description is omitted here.
Comparative example 4
The difference from example 1 is the arrangement of the electrolyte additive. The comparative example does not use isatoic anhydride as a functional additive and the mass fraction of the organic solvent is adjusted to 79.5%.
The rest is the same as embodiment 1, and the description is omitted here.
The performance of the sodium ion batteries obtained in the above examples 1 to 7 and comparative examples 1 to 4 is tested, and the test flow is as follows:
1) high temperature cycle life test
The sodium ion battery was charged at 45 ℃ to 4.2V at a constant current of 1C, charged at constant voltage to a cutoff current of 0.05C, and then discharged at a constant current of 1C to 1.5V, which was recorded as a charge-discharge cycle. Then, the cycle was performed under the above conditions, and when the capacity retention rate reached 80%, the number of cycles n was recorded, and the sodium ion battery capacity retention rate (%) (discharge capacity at the n-th cycle/first discharge capacity) × 100%.
2) Low temperature Performance test
Charging to 4.2V at a constant current and a constant voltage at a normal temperature by 1C, stopping charging at 0.05C, then discharging to 1.5V at a constant current by 1C, counting as initial capacity C0, then charging to 4.2V at a constant current and a constant voltage at a normal temperature by 1C, stopping charging at 0.05C, and placing in a low-temperature test cabinet for standing for 8 hours at-40 ℃ after full charging; at-40 ℃, 0.2C was discharged to 1.5V at constant current, and the discharge capacity C1 was recorded, the percent (%) discharge efficiency being C1/C0 × 100%.
3) Rate capability test
Charging to 4.2V at a constant current and a constant voltage at normal temperature at 1C, stopping charging at 0.05C, then discharging at a constant current at 1C to stop charging at 1.5V, and counting as initial capacity C0; then charging to 4.2V at constant current and constant voltage at room temperature under 1C, cutting off at 0.05C, discharging to 1.5V at constant current under 8C, recording discharge capacity C1, and the discharge efficiency (%) is C1/C0 × 100%
The results of the high temperature cycle performance test, the low temperature performance test, the rate performance test and the battery thickness expansion rate test are shown in table 1.
TABLE 1
Figure BDA0003716857070000081
From the table 1, it can be seen that the electrolyte of the present invention has better high-temperature cycle performance, low-temperature performance and high rate performance at high voltage compared to the electrolyte of the prior art, and the battery cell does not generate gas and deform at high voltage. From the comparison of example 1 with comparative examples 1 to 4, when the functional additives of fluorinated ethylene carbonate, vinyl sulfate, tris (trimethylsilane) borate and isatoic anhydride are set in the weight ratio of 5:1:0.5:0.5, the electrolyte has good performance, and has better high-voltage high-temperature cycle performance, high-voltage low-temperature performance and high-rate performance.
From the comparison of examples 1 to 5, it is shown that the electrolyte obtained has better properties when the isatoic anhydride accounts for 0.5% of the total mass of the electrolyte. Under the high voltage of 4.2V, the cycle number of high temperature of 45 ℃ and 1C/1C cycle capacity retention rate of 80% reaches up to 1362 circles, the battery thickness expansion rate is as low as 2.1%, the low temperature discharge efficiency of minus 40 ℃ reaches up to 79.3%, and the discharge efficiency of 8C reaches up to 75%, the performance is further optimized, and the electrolyte performance and effect are better.
As shown by comparing examples 1 and 6 to 7, the electrolyte obtained when 5-fluoroisatoic anhydride and 6-fluoroisatoic anhydride are used has better performance. Under the high voltage of 4.2V, the cycle number of the high temperature of 45 ℃ reaching 80% with the 1C/1C cycle capacity retention rate respectively reaches 1655 circles and 1671 circles, and the battery thickness expansion rate is respectively 1.2% and 1.3%, which is better than the performance of the embodiment 1; the discharge efficiency at the low temperature of minus 40 ℃ is respectively as high as 82.4 percent and 82.5 percent, the discharge efficiency at the low temperature of 8C is respectively as high as 78.7 percent and 78.5 percent, and the performance is more excellent.
Variations and modifications to the above-described embodiments may also occur to those skilled in the art, which fall within the scope of the invention as disclosed and taught herein. Therefore, the present invention is not limited to the above-mentioned embodiments, and any obvious improvement, replacement or modification made by those skilled in the art based on the present invention is within the protection scope of the present invention. Furthermore, although specific terms are employed herein, they are used in a generic and descriptive sense only and not for purposes of limitation.

Claims (10)

1. An electrolyte, which is characterized by comprising a conductive sodium salt, a non-aqueous organic solvent and a functional additive, wherein the functional additive comprises one or more of fluoroethylene carbonate, vinyl sulfate, isatoic anhydride/5-fluoroisatoic anhydride/6-fluoroisatoic anhydride and tris (trimethylsilane) borate.
2. The electrolyte of claim 1, wherein the functional additive comprises 1-10% of the total electrolyte mass.
3. The electrolyte of claim 1, wherein the conductive sodium salt comprises one or more of sodium hexafluorophosphate, sodium perchlorate, sodium difluorophosphate, and sodium bisoxalato.
4. The electrolyte of claim 1 or 3, wherein the conductive sodium salt is 12-18% of the total weight of the electrolyte.
5. The electrolyte of claim 1, wherein the non-aqueous organic solvent comprises one or more of cyclic carbonates, chain carbonates, ethyl propionate and propyl propionate.
6. The electrolyte according to claim 5, wherein the mass ratio of the cyclic carbonate to the chain carbonate is 1:1 to 4.
7. The electrolyte of claim 5, wherein the cyclic carbonate comprises one or a mixture of ethylene carbonate and propylene carbonate, and the chain carbonate comprises one or a mixture of dimethyl carbonate, diethyl carbonate and ethyl methyl carbonate.
8. The electrolyte according to any one of claims 5 to 7, wherein the non-aqueous organic solvent is present in an amount of 70 to 85% by mass based on the total mass of the electrolyte.
9. The electrolyte according to claim 1, wherein the functional additive is a mixture of fluoroethylene carbonate, vinyl sulfate, tris (trimethylsilane) borate and isatoic anhydride in a weight ratio of 2-8: 0.2-5: 0.1-5.
10. A sodium ion battery comprising the electrolyte of any one of claims 1-9.
CN202210738856.3A 2022-06-28 2022-06-28 Electrolyte and sodium ion battery Pending CN114976249A (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN116544510A (en) * 2023-05-19 2023-08-04 安徽理士新能源发展有限公司 Electrolyte with positive electrode film forming protection, preparation method and sodium ion battery

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN116544510A (en) * 2023-05-19 2023-08-04 安徽理士新能源发展有限公司 Electrolyte with positive electrode film forming protection, preparation method and sodium ion battery
CN116544510B (en) * 2023-05-19 2024-07-12 安徽理士新能源发展有限公司 Electrolyte with positive electrode film forming protection, preparation method and sodium ion battery

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