CN116207346A - Electrolyte for inhibiting circulation volume expansion of lithium metal secondary battery and preparation method thereof - Google Patents
Electrolyte for inhibiting circulation volume expansion of lithium metal secondary battery and preparation method thereof Download PDFInfo
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- CN116207346A CN116207346A CN202211724953.3A CN202211724953A CN116207346A CN 116207346 A CN116207346 A CN 116207346A CN 202211724953 A CN202211724953 A CN 202211724953A CN 116207346 A CN116207346 A CN 116207346A
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
- H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
- H01M10/0566—Liquid materials
- H01M10/0567—Liquid materials characterised by the additives
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/056—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
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The invention provides an electrolyte for inhibiting the circulation volume expansion of a lithium metal secondary battery and a preparation method thereof, wherein the electrolyte comprises the following components: the electrolyte comprises an ether organic solvent, a diluent, an additive and lithium salt, wherein the mass fraction of the additive in the electrolyte is 0.5-10%, and the concentration of the lithium salt is 1-6 mol/L. The preparation method of the electrolyte comprises the following steps: s1, adding the lithium salt into the ether organic solvent and the diluent under the protection of inert gas, and fully stirring until the solution is clear and transparent; and S2, adding the additive into the solution obtained in the step S1, and fully stirring until the solution is clear and transparent. The invention forms stable electrolyte interface film on the positive electrode and the negative electrode of the metal lithium secondary battery through the combined action of the ether organic solvent, the diluent, the additive and the lithium salt, so as to improve the cycle stability of the metal lithium secondary battery and inhibit the volume expansion of the metal lithium negative electrode.
Description
Technical Field
The invention relates to the technical field of preparation of metal lithium secondary batteries, in particular to electrolyte for inhibiting circulation volume expansion of a metal lithium secondary battery and a preparation method thereof.
Background
In recent years, the development of diversified energy demands has put higher demands on high energy density and long cycle life energy storage systems. The lithium metal negative electrode has been widely studied by researchers due to its high theoretical capacity density (3860 mAh/g) and negative electrode potential (-3.04V).
Although metallic lithium negative electrodes exhibit superior theoretical capacity and energy density, they have the following problems during application due to interfacial instability: (1) safety problems with lithium dendrite growth; (2) Irreversible side reactions lead to rapid loss of active material and rapid increase in cell resistance; (3) The "host-free" nature of metallic lithium results in pulverization of the electrode, causing unrestricted volume expansion and contraction during cycling. In order to solve the above problems and improve the interface stability of the lithium metal negative electrode, researchers respectively research from aspects of electrolyte modification, interface protection layer, structured electrode and the like, however, the implementation process of manually constructing the interface protection layer and the structured electrode is generally complex, and the related research is remained at the level of the small-area button cell negative electrode at present, so that large-area engineering application is difficult to realize, so that the optimization of the electrolyte adaptation of the lithium metal secondary battery is an effective means for improving the cycle stability of the lithium metal battery and inhibiting the volume expansion of the lithium negative electrode at present.
Disclosure of Invention
The invention aims to provide an electrolyte for inhibiting the circulation volume expansion of a metal lithium secondary battery and a preparation method thereof, wherein a stable electrolyte interface film is formed on a positive electrode and a negative electrode of the metal lithium battery through the combined action of an ether organic solvent, a diluent, an additive and lithium salt so as to improve the circulation stability of the metal lithium battery and inhibit the volume expansion of the metal lithium negative electrode.
The technical scheme adopted by the invention is as follows: an electrolyte for suppressing cycle volume expansion of a lithium metal secondary battery, the electrolyte comprising: the electrolyte comprises an ether organic solvent, a diluent, an additive and lithium salt, wherein the mass fraction of the additive in the electrolyte is 0.5-10%, and the concentration of the lithium salt is 1-6 mol/L.
Further, the melting temperature of the electrolyte is-20-80 ℃, and the ionic conductivity is 1 mS/cm-10 mS/cm.
Further, the ether-type organic solvent comprises at least one of ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, triethylene glycol dimethyl ether, tetraethylene glycol dimethyl ether, diethylene glycol diethyl ether and triethylene glycol diethyl ether.
Further, the diluent comprises a compound having the structure R 1 -O-R 2 Wherein R is a compound of formula (I) 1 And R is 2 Each independently represents a fluoroalkyl group having 1 to 6 carbon atoms.
Further, the method comprises the steps of, the diluent comprises 1, 2-tetrafluoroethyl-2, 2-trifluoroethyl ether, perfluor nonenyl trifluoroethyl ether 1, 2-tetrafluoroethyl-2, 3-tetrafluoropropyl ether at least one of 1H, 5H-octafluoropentyl-1, 2-tetrafluoroethyl ether.
Further, the additive comprises at least one of 1, 3-propane sultone, 1, 3-propylene sultone, ethylene sulfate, vinylene carbonate, triphenyl phosphite, tris (trimethylsilane) phosphate and tris (trimethylsilane) borate.
Further, the lithium salt comprises one or two of lithium difluorophosphate, lithium hexafluorophosphate, lithium bistrifluoromethane sulfonyl imide, lithium bistrifluorosulfonyl imide, lithium difluorooxalato borate and lithium dioxaoxalato borate.
The invention also provides a preparation method of the electrolyte for inhibiting the circulation volume expansion of the metal lithium secondary battery, which comprises the following steps:
s1, adding the lithium salt into the ether organic solvent and the diluent under the protection of inert gas, and fully stirring until the solution is clear and transparent;
and S2, adding the additive into the solution obtained in the step S1, and fully stirring until the solution is clear and transparent.
Further, the volume ratio of the ether-type organic solvent to the diluent is 1:1.
Further, the preparation temperature of the electrolyte is 25-40 ℃, and the stirring time is 0.5-3 h.
The invention has the beneficial effects that: the electrolyte forms an interfacial film on the surfaces of the positive electrode and the negative electrode of the lithium metal secondary battery by the combined action of the additive, the ether-type organic solvent, the diluent and the lithium salt. Wherein:
(1) The electrolyte interface film (CEI) with stable high potential generated on the surface of the positive electrode can effectively inhibit the dissolution of the positive electrode transition metal of the metal lithium secondary battery in the long-life cycle process, effectively improve the capacity retention rate of the battery and improve the cycle stability of the battery;
(2) The solid electrolyte interface film (SEI) is formed on the surface of the negative electrode, the LiF has higher surface energy, lithium can be promoted to be densely deposited along the surface of the negative electrode, dendritic and spongy lithium deposition is reduced, the SEI film can effectively improve the interface stability of the negative electrode of the metal lithium battery, and effectively inhibit the expansion of the negative electrode of the metal lithium battery in the circulating process, so that the volume expansion of the metal lithium secondary battery in the long-life circulating process is inhibited, and the circulating stability of the battery and the group rate of the battery module are improved.
In addition, the preparation method of the electrolyte provided by the invention has simple process and high preparation efficiency, provides an engineering scheme in the practical application of the metal lithium secondary battery, greatly improves the overall performance of the metal lithium secondary battery, is beneficial to improving the market application prospect of the battery, and has great production practice significance.
Drawings
FIG. 1 is a graph showing the expansion ratio of the infinite loop thickness of a lithium secondary battery using the electrolytes of examples 1 to 2 and comparative examples;
FIG. 2 is a graph showing the comparison of internal stress in cycles of lithium metal secondary batteries using the electrolytes of examples 1-2 and comparative examples;
fig. 3 is a graph of the cycle capacity retention rate of the lithium metal secondary batteries using the electrolytes of examples 1-2 and comparative examples.
Detailed Description
Embodiments of the present invention are described in detail below, examples of which are illustrated in the accompanying drawings, wherein like or similar reference numerals refer to like or similar elements or elements having like or similar functions throughout. The embodiments described below by referring to the drawings are illustrative and intended to explain the present invention and should not be construed as limiting the invention.
The embodiment of the invention provides an electrolyte for inhibiting the circulation volume expansion of a lithium metal secondary battery, which comprises the following components: the electrolyte comprises an ether organic solvent, a diluent, an additive and lithium salt, wherein the mass fraction of the additive is 0.5-10%, and the concentration of the lithium salt is 1-6 mol/L. The additive is used for matching with ether organic solvent, diluent and lithium salt to form an interfacial film on the surface of an electrode of a metal lithium secondary battery, the interfacial film generated by too little additive is too thin and easy to crack, the transition metal dissolution of the positive electrode and the volume expansion of the negative electrode cannot be effectively inhibited, and the interfacial film generated by too much additive is too thick, so that the impedance and polarization of the battery can be increased, and the discharge capacity of the battery can be reduced; too low a concentration of lithium salt affects the conductivity of the electrolyte and too high a concentration increases the viscosity of the electrolyte.
In some embodiments, the electrolyte has a melting temperature of-20 ℃ to 80 ℃ and an ionic conductivity of 1mS/cm to 10mS/cm.
In some embodiments, the ether-based organic solvent comprises at least one of ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, triethylene glycol dimethyl ether, tetraethylene glycol dimethyl ether, diethylene glycol diethyl ether, triethylene glycol diethyl ether. Preferably, the ether organic solvent is selected from ethylene glycol dimethyl ether and triethylene glycol dimethyl ether.
In some embodiments, the diluent comprises a structure of R 1 -O-R 2 Wherein R is a compound of formula (I) 1 And R is 2 Each independently represents a fluoroalkyl group having 1 to 6 carbon atoms; in particular to a special-shaped ceramic tile, comprises 1, 2-tetrafluoroethyl-2, 2-trifluoroethyl ether, perfluoro nonenyl trifluoroethyl ether 1, 2-tetrafluoroethyl-2, 3-tetrafluoropropyl ether at least one of 1H, 5H-octafluoropentyl-1, 2-tetrafluoroethyl ether. Preferably, the diluent is 1, 2-tetraFluoroethyl-2, 2-trifluoroethyl ether. The electrolyte containing the diluent generates a fluoride (LiF) solid electrolyte interface film (SEI) rich in inorganic lithium salt on a metal lithium negative electrode, liF has higher surface energy, can promote lithium to be densely deposited along the surface of the negative electrode, reduces dendritic and spongy lithium deposition, can effectively improve the interface stability of the negative electrode, and effectively inhibit the expansion of the metal lithium negative electrode in the circulating process, thereby inhibiting the volume expansion of a metal lithium secondary battery in the long-life circulating process, and improving the circulating stability of the battery and the group rate of a battery module.
In some embodiments, the additive comprises at least one of 1, 3-propane sultone, ethylene sulfate, vinylene carbonate, triphenyl phosphite, tris (trimethylsilane) phosphate, tris (trimethylsilane) borate. Under the combined action of the additive, the ether organic solvent, the diluent and the lithium salt, an interface film is formed on the surfaces of the anode and the cathode of the metal lithium secondary battery, wherein the electrolyte interface film (CEI) with stable high potential generated on the surface of the anode can effectively inhibit the dissolution of the transition metal of the anode of the metal lithium secondary battery in the long-life cycle process, effectively improve the capacity retention rate of the battery and improve the cycle stability of the battery.
In some embodiments, the lithium salt comprises one or two of lithium difluorophosphate, lithium hexafluorophosphate, lithium bistrifluoromethane sulfonimide, lithium bistrifluorosulfonyl imide, lithium difluorooxalato borate, lithium dioxaoxalato borate.
The embodiment of the invention also provides a preparation method of the electrolyte for inhibiting the circulation volume expansion of the metal lithium secondary battery, which comprises the following steps:
s1, under the protection of inert gas, adding lithium salt into an ether organic solvent and a diluent, and fully stirring until the solution is clear and transparent;
and S2, adding an additive into the solution obtained in the step S1, and fully stirring until the solution is clear and transparent.
In some embodiments, the volume ratio of the ether-based organic solvent to the diluent is 1:1.
Since lithium salts are susceptible to thermal decomposition, the temperature of the electrolyte and the duration of stirring should be controlled when preparing the electrolyte. In some embodiments, the electrolyte is prepared at a temperature of 25℃to 40℃and stirred for a period of 0.5h to 3h.
The electrolyte prepared by the embodiment and the comparative example of the invention adopts the structure of a metal lithium secondary battery for performance test, and the metal lithium secondary battery comprises an anode, a cathode, a diaphragm, an aluminum plastic film and electrolyte; the positive electrode is a nickel cobalt lithium manganate positive electrode, a lithium cobaltate positive electrode or a lithium-rich manganese-based oxide positive electrode; the negative electrode is a metal lithium belt, a metal lithium magnesium alloy, a metal lithium aluminum alloy or a metal lithium boron alloy; the diaphragm is a single-layer polypropylene diaphragm, a three-layer polypropylene-polyethylene composite diaphragm or a polypropylene-alumina ceramic coating composite diaphragm.
The invention has been subjected to a plurality of experiments in succession, and the invention is further described in detail by referring to some experimental results, and the detailed description is provided below in connection with specific examples.
Example 1:
preparing an electrolyte for inhibiting the cycle volume expansion of the lithium metal secondary battery:
s1, magnetically stirring ethylene glycol dimethyl ether, triethylene glycol dimethyl ether and 1, 2-tetrafluoroethyl-2, 2-trifluoroethyl ether for 0.5h in an argon atmosphere glove box according to the volume ratio of 1:1:2 at 25 ℃ to uniformly mix the materials; then adding lithium bistrifluoromethane yellow imide into the solution at the molar concentration of 4mol/L, and stirring the solution for 2 hours at the temperature of 30 ℃ by using a magnetic stirrer until the lithium salt is completely dissolved, and the solution is clear and transparent;
and s2, adding vinylene carbonate which accounts for 2% of the total mass of the prepared electrolyte into the solution obtained in the step s1, and stirring for 1h at 25 ℃ by using a magnetic stirrer until the solution is clear and transparent, thus obtaining the electrolyte.
Preparing a metal lithium secondary battery:
uniformly dispersing 97 wt% of positive electrode active material nickel cobalt lithium manganate (NCM 811), 1wt% of conductive carbon black, a conductive agent consisting of 0.5wt% of conductive agent carbon nano tube and 1.5wt% of binder PVDF in a proper amount of NMP solvent through a refiner, wherein the PVDF accounts for 5wt% in the NMP solvent; and coating the uniformly dispersed slurry on an aluminum foil current collector to prepare a positive electrode, and slitting and rolling to obtain the positive electrode plate of the metal lithium secondary battery.
After cutting a metal lithium strip with the thickness of 0.06mm into a proper size, pressing a copper tab on the lithium strip by using an oil press at a fixed position, and pressing a lithium strip with the same size and thickness on one side of the lithium strip covered by the copper tab to supplement lithium so as to avoid capacity loss at the covered position of the copper tab, thereby obtaining the negative electrode plate of the metal lithium secondary battery.
And sequentially stacking the negative electrode plate, the polypropylene-alumina ceramic coating composite diaphragm and the positive electrode plate in sequence in a lamination mode to obtain a metal lithium secondary battery cell, packaging by using a lithium battery grade aluminum-plastic film, and preparing the metal lithium secondary battery through the technological processes of liquid injection (the injection amount of the electrolyte prepared by injection is 1.5 g/Ah), infiltration, formation, degassing and the like.
Performance test:
the charge-discharge cycle performance test was performed at a rate of 0.2C using a charge-discharge apparatus, with a charge cutoff voltage of 4.4V and a discharge cutoff voltage of 2.75V.
Example 2:
the difference from example 1 is a method of preparing an electrolyte that suppresses the cycle volume expansion of a lithium metal secondary battery. The preparation and performance test of the lithium metal secondary battery in this example were identical to those of example 1.
In this embodiment, the step of preparing an electrolyte that suppresses the cycle volume expansion of the lithium metal secondary battery includes:
s1, magnetically stirring ethylene glycol dimethyl ether, triethylene glycol dimethyl ether and 1, 2-tetrafluoroethyl-2, 2-trifluoroethyl ether for 0.5h in an argon atmosphere glove box according to the volume ratio of 1:1:2 at 25 ℃ to uniformly mix the materials; then adding lithium bistrifluoromethane yellow imide into the solution at the molar concentration of 4mol/L, and stirring the solution for 2 hours at the temperature of 30 ℃ by using a magnetic stirrer until the lithium salt is completely dissolved, and the solution is clear and transparent;
and s2, adding vinylene carbonate and lithium difluorophosphate into the solution obtained in the step s1, wherein the vinylene carbonate accounts for 2% of the total mass of the prepared electrolyte, the lithium difluorophosphate accounts for 1% of the total mass of the prepared electrolyte, and stirring for 1h at 25 ℃ by using a magnetic stirrer until the solution is clear and transparent, thus obtaining the electrolyte.
Comparative example:
the difference from example 1 is that the present comparative example uses the current commonly used preparation method to prepare the electrolyte. The preparation and performance test of the lithium metal secondary battery in this comparative example were identical to those of example 1.
In this comparative example, the step of preparing an electrolyte solution includes: in an argon atmosphere glove box, lithium hexafluorophosphate is added into a mixed solvent of fluoroethylene carbonate and methyl ethyl carbonate (the volume ratio of the fluoroethylene carbonate to the methyl ethyl carbonate is 1:2) at a molar concentration of 1mol/L, and the mixture is stirred for 1h at 30 ℃ by using a magnetic stirrer until lithium salt is completely dissolved, and the solution is clear and transparent. Then adding 1, 2-tetrafluoroethyl-2, 2-trifluoroethyl ether into the solution obtained by the above operation, wherein 1, 2-tetrafluoroethyl-2, 2-trifluoroethyl ether accounts for 10% of the total mass of the electrolyte, and the electrolyte is stirred for 1h at 25 ℃ by using a magnetic stirrer.
The test results of example 1, example 2 and comparative example were subjected to comparative analysis, and the comparative results were referred to fig. 1 to 3.
Expansion ratio contrast of infinite loop thickness of lithium secondary battery: as can be seen from fig. 1, the batteries using the electrolytes of examples 1 and 2 have lower thickness expansion rates and lower cycle volume changes under the same charge-discharge regimes than the batteries using the electrolytes of the comparative examples. The battery using the electrolyte in example 1 was cycled for 22 weeks under infinite free expansion conditions, the full state thickness expansion rate was only 40.8%, the battery using the electrolyte in example 2 was cycled for 22 weeks under infinite free expansion conditions, the full state thickness expansion rate was only 30.9%, and the battery using the electrolyte in comparative example was cycled the same number of times under the same conditions, the full state thickness expansion rate was as high as 60.7%. This is because the electrolytes in examples 1 and 2 have an effect of generating a stable and dense SEI film on the surface of a lithium metal negative electrode, avoiding repeated consumption and regeneration of the SEI film, and effectively weakening side reactions between the lithium metal negative electrode and the electrolyte, inhibiting growth of lithium dendrites and formation of sponge-like pulverized lithium, and effectively inhibiting volume expansion of the lithium metal secondary battery during circulation.
Comparison of internal stress in cycle of lithium metal secondary battery: as can be seen from fig. 2, under the same charge-discharge regime, the batteries using the electrolytes of example 1 and example 2 have low internal cyclic expansion stress compared to the batteries using the electrolytes of comparative examples, and have mechanical advantages for the subsequent modular lightening of the batteries. The full state maximum expansion force of the battery using the electrolyte in example 1 was 1139.3kg, the full state maximum expansion force of the battery using the electrolyte in example 2 was 1073.8kg, and the full state maximum expansion force of the battery using the electrolyte in comparative example was 1387.7kg, at 15 weeks of the cycle. This is because the SEI films generated on the surface of the metallic lithium negative electrode by the electrolytes in examples 1 and 2 have more excellent inhibition effect on the expansion of the lithium negative electrode.
Comparison of the cycle capacity retention ratio of the lithium metal secondary battery: as can be seen from fig. 3, the batteries using the electrolytes of example 1 and example 2 have more excellent cycle stability than the batteries using the electrolytes of comparative examples under the same charge-discharge regimes. The batteries using the electrolytes of examples 1 and 2 still have a capacity retention rate of 90% or more after being stably circulated in a lean state for 70 weeks, whereas the batteries using the electrolytes of comparative examples exhibit a capacity jump phenomenon only after being circulated for 30 weeks. This is because the electrolyte prepared in example 1 and example 2 generates a high potential stable CEI film on the surface of the positive electrode of the battery, and generates a high interface stability SEI film on the surface of the negative electrode of the lithium metal, which can effectively inhibit side reactions caused by dissolution of the transition metal of the positive electrode during long-life cycle of the lithium metal secondary battery, and inhibit volume expansion caused by pulverization of the lithium metal, thereby effectively improving the capacity retention rate of the battery and the cycle stability of the battery.
Compared with the prior art, the electrolyte for inhibiting the volume expansion of the metal lithium secondary battery provided by the invention has obvious effects of improving the interface stability of the positive electrode and the negative electrode of the metal lithium and inhibiting the volume expansion of the negative electrode of the metal lithium, and can effectively improve the cycle stability and the module grouping rate of the metal lithium secondary battery; the preparation method of the electrolyte provided by the invention has the advantages of simple process and high preparation efficiency, provides an engineering scheme in the practical application of the metal lithium secondary battery, greatly improves the overall performance of the metal lithium secondary battery, is beneficial to improving the market application prospect of the battery, and has great production practice significance.
It is to be understood that the above-described embodiments of the present invention are merely illustrative of or explanation of the principles of the present invention and are in no way limiting of the invention. Accordingly, any modification, equivalent replacement, improvement, etc. made without departing from the spirit and scope of the present invention should be included in the scope of the present invention. Furthermore, the appended claims are intended to cover all such changes and modifications that fall within the true scope and boundary of the claims, or equivalents of such scope and boundary.
Claims (10)
1. An electrolyte for suppressing expansion of a cycle volume of a lithium metal secondary battery, the electrolyte comprising: the electrolyte comprises an ether organic solvent, a diluent, an additive and lithium salt, wherein the mass fraction of the additive in the electrolyte is 0.5-10%, and the concentration of the lithium salt is 1-6 mol/L.
2. The electrolyte for suppressing the cyclic volume expansion of a lithium metal secondary battery according to claim 1, wherein the melting temperature of the electrolyte is-20 ℃ to 80 ℃ and the ionic conductivity is 1mS/cm to 10mS/cm.
3. The electrolyte for suppressing the cycle volume expansion of a lithium metal secondary battery according to claim 1, wherein the ether-based organic solvent comprises at least one of ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, triethylene glycol dimethyl ether, tetraethylene glycol dimethyl ether, diethylene glycol diethyl ether, triethylene glycol diethyl ether.
4. The electrolyte for suppressing cycle volume expansion of a lithium metal secondary battery as recited in claim 1, which comprisesCharacterized in that the diluent comprises a compound of the formula R 1 -O-R 2 Wherein R is a compound of formula (I) 1 And R is 2 Each independently represents a fluoroalkyl group having 1 to 6 carbon atoms.
5. The electrolyte for suppressing the cycle volume expansion of a lithium metal secondary battery according to claim 4, the diluent comprises 1, 2-tetrafluoroethyl-2, 2-trifluoroethyl ether, perfluor nonenyl trifluoroethyl ether 1, 2-tetrafluoroethyl-2, 3-tetrafluoropropyl ether at least one of 1H, 5H-octafluoropentyl-1, 2-tetrafluoroethyl ether.
6. The electrolyte for suppressing the cycle volume expansion of a lithium metal secondary battery according to claim 1, wherein the additive comprises at least one of 1, 3-propane sultone, ethylene sulfate, vinylene carbonate, triphenyl phosphite, tris (trimethylsilane) phosphate, tris (trimethylsilane) borate.
7. The electrolyte for suppressing the cycle volume expansion of a lithium metal secondary battery according to claim 1, wherein the lithium salt comprises one or two of lithium difluorophosphate, lithium hexafluorophosphate, lithium bistrifluoro-methanesulfonimide, lithium bistrifluoro-sulfimide, lithium difluorooxalato-borate, and lithium dioxaato-borate.
8. The method for preparing an electrolyte for suppressing the cycle volume expansion of a lithium metal secondary battery according to any one of claims 1 to 7, comprising the steps of:
s1, adding the lithium salt into the ether organic solvent and the diluent under the protection of inert gas, and fully stirring until the solution is clear and transparent;
and S2, adding the additive into the solution obtained in the step S1, and fully stirring until the solution is clear and transparent.
9. The method for producing an electrolyte for suppressing the cycle volume expansion of a lithium metal secondary battery according to claim 8, wherein the volume ratio of the ether-based organic solvent to the diluent is 1:1.
10. The method for preparing an electrolyte for suppressing the cycle volume expansion of a lithium metal secondary battery according to claim 8, wherein the electrolyte is prepared at a temperature of 25-40 ℃ and stirred for 0.5-3 h.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116505079A (en) * | 2023-06-13 | 2023-07-28 | 福州大学 | Electrolyte for metal lithium secondary battery, preparation method of electrolyte and metal lithium secondary battery |
| CN116799312A (en) * | 2023-08-23 | 2023-09-22 | 宁德时代新能源科技股份有限公司 | Secondary battery, electrolyte and electricity using device |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116505079A (en) * | 2023-06-13 | 2023-07-28 | 福州大学 | Electrolyte for metal lithium secondary battery, preparation method of electrolyte and metal lithium secondary battery |
| CN116799312A (en) * | 2023-08-23 | 2023-09-22 | 宁德时代新能源科技股份有限公司 | Secondary battery, electrolyte and electricity using device |
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