CN112382792A - Fluoroether-containing electrolyte cosolvent for lithium metal/lithium ion/lithium sulfur battery, electrolyte and lithium secondary battery - Google Patents
Fluoroether-containing electrolyte cosolvent for lithium metal/lithium ion/lithium sulfur battery, electrolyte and lithium secondary battery Download PDFInfo
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- 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
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Abstract
The invention discloses a fluorine-containing ether electrolyte cosolvent for a lithium metal/lithium ion/lithium sulfur battery, an electrolyte and a lithium secondary battery. The electrolyte cosolvent provided by the invention comprises a fluorine-containing ether compound. The molecular structural formula of the fluorine-containing ether compound is shown in formulas (I) to (VI); the fluorine-containing ether compound has the advantages of wide electrochemical stability window, stability to lithium metal and the like, and can be used for preparing a lithium secondary battery, so that the capacity retention rate and the cycle stability of the obtained lithium secondary battery can be remarkably improved; has better application prospect in the field of lithium batteries.
Description
Technical Field
The invention belongs to the technical field of battery materials, and particularly relates to a fluorine-containing ether electrolyte cosolvent for a lithium metal/lithium ion/lithium sulfur battery, an electrolyte and a lithium secondary battery.
Background
The electrolyte is known as 'blood' in the lithium battery, and plays an important role in the capacity exertion of the lithium battery electrode material, the battery circulation stability, the battery safety and the like. The electrolyte used in the conventional lithium ion battery is generally prepared by using Ethylene Carbonate (EC), Ethyl Methyl Carbonate (EMC), dimethyl carbonate (DMC), diethyl carbonate (DEC) and the like as main solvents, and lithium hexafluorophosphate as a lithium salt and adding a certain amount of additives. The electrolyte can form a relatively stable Solid Electrolyte Interface (SEI) on the graphite negative electrode, and can protect the graphite negative electrode from being peeled off in the circulation process, so that good circulation stability is achieved. Meanwhile, the electrolyte has moderate oxidation resistance potential and is relatively stable to positive electrode materials such as lithium iron phosphate, nickel cobalt lithium manganate, lithium cobaltate, lithium manganate and the like, so that the electrolyte can play a wide role in the field of lithium ion batteries.
However, due to the continuous pursuit of high specific energy lithium batteries and the lower theoretical specific capacity (372mAh/g) of graphite negative electrodes, the attention of negative electrode materials is shifted to lithium metal materials with higher specific capacity and lower potential (3860mAh/g, -3.04V vs. SHE). For the traditional carbonate electrolyte, the carbonate electrolyte is not suitable for a lithium metal battery, mainly because the potential of lithium metal is low, the reducibility is strong, and the carbonate electrolyte can react with most of ester electrolytes, so that the growth of lithium dendrites and the formation of dead lithium are easily caused in the charging and discharging processes, and finally, the battery is rapidly attenuated, and the requirement is difficult to meet. In addition, since lithium polysulfide can also chemically react with an ester electrolyte, conventional ester electrolytes are also difficult to use in lithium sulfur batteries.
Recently, the subject group of the professor Wangchun university of Maryland selects an inert solvent OFE as a cosolvent (Zheng J., Ji G, et al, high-Fluorinated Electrolytes for Li-S Batteries [ J ]. Advanced Energy Materials,2019,9 (16)), and by introducing OFE with a certain volume ratio into LiFSI/DME electrolyte, the viscosity of the electrolyte can be reduced, the wettability of the electrolyte can be improved, and the characteristics of high-concentration electrolyte can be maintained under the condition of lower lithium salt dosage. However, the ether electrolyte system has a low oxidative decomposition potential, and is difficult to meet the requirements of high-voltage cathode materials (such as lithium iron phosphate LFP, ternary cathode materials NCM, spinel lithium nickel manganese oxide and other cathode materials). Meanwhile, OFE is too expensive to be commercially applied.
Disclosure of Invention
In order to overcome the defects of the prior art, the invention aims to provide a fluorine-containing ether electrolyte cosolvent for a lithium metal/lithium ion/lithium sulfur battery, an electrolyte and a lithium secondary battery.
The invention aims to provide a fluorine-containing ether compound and a preparation method thereof, a fluorine-containing ether electrolyte cosolvent for a lithium metal/lithium ion/lithium sulfur battery, an electrolyte and a secondary battery, and aims to solve the technical problems of poor stability, low oxidative decomposition potential and the like of the existing ester electrolyte and ether electrolyte.
The purpose of the invention is realized by at least one of the following technical solutions.
The invention provides a fluorine-containing ether electrolyte cosolvent (inert electrolyte cosolvent) for a lithium metal/lithium ion/lithium sulfur battery, which comprises a fluorine-containing ether compound; the structural formula of the fluorine-containing ether compound is more than one of the following formulas (I) to (VI):
further, the preparation method of the fluorine-containing ether compound comprises the following steps:
(1) mixing p-toluenesulfonyl chloride, fluorine alcohol and alkali metal hydroxide to generate p-toluenesulfonate from the p-toluenesulfonyl chloride and the fluorine alcohol;
(2) and mixing the p-toluenesulfonate, the fluoroalcohol and the alkali metal hydroxide again, reacting the fluoroalcohol with the alkali metal hydroxide to generate fluoroalcohol organic base, and carrying out bimolecular nucleophilic substitution reaction on the fluoroalcohol organic base and the p-toluenesulfonate to generate the fluorine-containing ether compound.
Further, the alkali metal hydroxide in the step (1) is more than one of sodium hydroxide and potassium hydroxide; the molar ratio of the p-toluenesulfonyl chloride to the fluoroalcohol to the alkali metal hydroxide is 1:1:1 to 1:1: 3.
Further, the temperature of the mixing treatment in the step (1) is-5 ℃ to 10 ℃.
Further, the molar ratio of the p-toluenesulfonate, the fluoroalcohol and the alkali metal hydroxide in the step (2) is 1:1:1 to 1:1: 3.
Further, the temperature of the mixing treatment in the step (2) is-5 ℃ to 10 ℃; the temperature of bimolecular nucleophilic substitution reaction in the step (2) is 30-60 ℃; the time of bimolecular nucleophilic substitution reaction is 3h-8 h.
Preferably, the molecular structural formula of the fluoroalcohol is any one of the formulas (i) - (iii).
The electrolyte provided by the invention comprises the fluorine-containing ether electrolyte cosolvent for the lithium metal/lithium ion/lithium sulfur battery.
The electrolyte provided by the invention also comprises more than one of electrolyte and additive; the electrolyte is at least one of lithium hexafluorophosphate, lithium bis (trifluoromethyl) sulfonyl imide and lithium bis (fluoro) sulfonyl imide; the concentration of the electrolyte is 0.5-4 mol/L; the additive is at least one of fluoroethylene carbonate, ethylene sulfate and vinylene carbonate; the mass of the additive accounts for 0.2-5% of the total mass of the electrolyte.
The lithium secondary battery provided by the invention comprises the electrolyte.
Compared with the prior art, the invention has the following advantages and beneficial effects:
(1) in the electrolyte cosolvent provided by the invention, fluorine is used for replacing hydrogen in the molecular structure of the fluorine-containing ether compound, so that the highest bonding occupied molecular orbital energy level (HOMO) of the fluorine-containing ether compound can be reduced, and the oxidation resistance potential of the fluorine-containing ether compound is improved; meanwhile, the higher fluorine content can also reduce the flammability of the fluorine-containing ether compound;
(2) in the preparation method of the fluorine-containing ether compound, high fluorine-containing functional groups can be introduced into the ether compound by simply mixing and treating the p-toluenesulfonate, the polyfluorool and the alkali metal hydroxide and carrying out bimolecular nucleophilic substitution reaction. In addition, the preparation method of the fluorine-containing ether compound also has the advantages of cheap and easily obtained raw materials, simple and easy preparation process, mild conditions and the like;
(3) the electrolyte comprises the inert electrolyte cosolvent, and because the fluorine-containing ether compound in the inert cosolvent has higher oxidation-resistant potential, the oxidation reaction at the final charging stage can be avoided, and the high-voltage stability of the electrolyte is improved; secondly, the fluorine-containing ether compound has higher fluorine content, so that the flammability of the electrolyte can be reduced, and the safety of the electrolyte can be improved; finally, the high-content fluorine atoms can be decomposed on the surface of the lithium metal negative electrode to generate lithium fluoride, so that the lithium metal is stabilized, and the growth of lithium dendrites is inhibited;
(4) the lithium secondary battery of the present invention comprises the above electrolyte, and thus has more excellent high voltage stability and safety; the lithium secondary battery has the advantages that the attenuation of the battery capacity is slowed down by stabilizing lithium metal and inhibiting the growth of lithium dendrite, and the shuttle effect of irreversible loss of active substances and capacity caused by the fact that lithium polysulfide is dissolved in electrolyte and diffuses to a negative electrode is avoided by reducing the solubility of the lithium polysulfide in the electrolyte, so that the cycle stability of the obtained lithium secondary battery is remarkably improved.
Drawings
FIG. 1 shows an embodiment of the present invention in which an electrolyte is used to form a lithium copper half cell at 0.5mA/cm2Current density of 1mAh/cm2The results of 100 cycles under the surface volume conditions are shown schematically.
Fig. 2 is a schematic diagram of the result of 100 cycles of a lithium battery made of the electrolyte and the LFP as the positive electrode material under the condition of 0.5C according to an embodiment of the present invention.
FIG. 3 shows an embodiment of the present invention, wherein the electrolyte is used to form a lithium copper half cell at 1mA/cm2Current density of 1mAh/cm2Results under the conditions of surface capacity are shown schematically.
Fig. 4 is a graph showing the results of 100 cycles of the lithium sulfur battery made of the electrolyte and the sulfur cathode material according to one embodiment of the present invention under 0.5C.
FIG. 5 shows a state that the electrolyte solution obtained in one embodiment of the present invention is used to prepare a lithium copper half cell at 1mA/cm2Current density of 1mAh/cm2The results of 100 cycles under the surface volume conditions are shown schematically.
Fig. 6 is a schematic diagram of the electrolyte obtained in one embodiment of the present invention and the result of 100 cycles of the lithium battery made of the positive electrode material NCM622 under the condition of 0.5C.
Fig. 7 is a schematic diagram of capacity retention rate of 100 cycles of a lithium battery prepared by using the electrolyte obtained in one comparative example and LFP as a positive electrode material under the condition of 0.5C.
Detailed Description
The following description of the embodiments of the present invention is provided in connection with the accompanying drawings and examples, but the invention is not limited thereto. It is noted that the processes described below, if not specifically described in detail, are all realizable or understandable by those skilled in the art with reference to the prior art. The reagents or apparatus used are not indicated to the manufacturer, and are considered to be conventional products available by commercial purchase.
In the description of the present invention, it should be understood that the weight of the related components mentioned in the embodiments of the present invention may not only refer to the specific content of each component, but also represent the proportional relationship of the weight among the components, and therefore, it is within the scope of the disclosure that the content of the related components is scaled up or down according to the embodiments of the present invention. Specifically, the weight described in the embodiments of the present invention may be a unit of mass known in the chemical field such as μ g, mg, g, kg, etc.
In the description of the invention, an expression of a word in the singular should be understood to include the plural of the word, unless the context clearly dictates otherwise. The terms "comprises" or "comprising" are intended to specify the presence of stated features, quantities, steps, operations, elements, portions, or combinations thereof, but are not intended to preclude the presence or addition of one or more other features, quantities, steps, operations, elements, portions, or combinations thereof.
The fluorine content in the molecular structure of the fluorine-containing ether compound provided by the embodiment of the invention is higher, so that the highest bonding occupied molecular orbital energy level (HOMO) of the fluorine-containing ether compound can be reduced, and the oxidation resistance potential of the fluorine-containing ether compound is improved; can also reduce the flammability of the fluorine-containing ether compound.
The fluorine-containing ether compound provided by the embodiment of the invention can be prepared by the following method.
Correspondingly, the embodiment of the invention also provides a preparation method of the fluorine-containing ether compound, which comprises the following steps:
s1, providing p-toluenesulfonyl chloride, fluoroalcohol and alkali metal hydroxide; mixing p-toluenesulfonyl chloride with fluoroalcohol and alkali metal hydroxide to produce p-toluenesulfonate.
S2, mixing the p-toluenesulfonate with fluoroalcohol and alkali metal hydroxide for treatment, reacting the fluoroalcohol with the alkali metal hydroxide to generate fluoroalcohol organic base, and carrying out bimolecular nucleophilic substitution reaction on the fluoroalcohol organic base and the p-toluenesulfonate to generate the fluorine-containing ether compound (named DFE);
the molecular structural formula of the fluorine-containing ether compound is shown in formulas (I) to (VII):
in the preparation method of the fluorine-containing ether compound provided by the embodiment of the invention, the p-toluenesulfonate, the fluoroalcohol and the alkali metal hydroxide are simply mixed and subjected to bimolecular nucleophilic substitution reaction, so that the high fluorine-containing functional group can be introduced into the ether compound. In addition, the preparation method of the fluorine-containing ether compound provided by the embodiment of the invention also has the advantages of cheap and easily available raw materials, simple and easy preparation process, mild conditions and the like.
The fluorine alcohol is used for providing fluorine atoms for the fluorine-containing ether compound in the embodiment of the invention and providing alcoholic hydroxyl groups for the subsequent bimolecular nucleophilic substitution reaction. In some embodiments, the fluoroalcohol is specifically selected from any one of the molecular structural formulas shown in formulas (i) - (iii):
in bimolecular nucleophilic substitution reactions, a nucleophile is required to provide an electron, and since the electron is provided by a base, the nucleophile should generally be basic, and bimolecular nucleophilic substitution reactions should also be performed under basic conditions. In embodiments of the invention, an alkali metal hydroxide is used to react with the fluoroalcohol to form the fluoroalcohol organic base, thereby providing an alkaline reaction environment and electrons for bimolecular nucleophilic substitution reactions. In some embodiments, the alkali metal hydroxide is selected from at least one of lithium hydroxide, sodium hydroxide and potassium hydroxide, preferably lithium hydroxide, sodium hydroxide or potassium hydroxide solution with mass concentration of 40% -60%, and has the advantages of strong alkalinity, low cost and easily available materials.
In S2, p-toluenesulfonate, fluoroalcohol and alkali metal hydroxide are mixed and treated, the fluoroalcohol reacts with the alkali metal hydroxide to generate fluoroalcohol organic base, and then the fluoroalcohol organic base reacts with the p-toluenesulfonate to perform bimolecular nucleophilic substitution reaction. By controlling the reaction temperature, the reactions can be further promoted to occur in the above order, and the reaction rate can be increased. In some examples, the molar ratio of p-toluenesulfonate, polyfluorool and alkali metal hydroxide is 1:1:1 to 1:1:3 when the p-toluenesulfonate, polyfluorool and alkali metal hydroxide are mixed, and the reaction is ensured to be complete by adding an excess of base.
In some embodiments, by controlling the reaction temperature between-5 ℃ and 10 ℃, the fluoroalcohol can be promoted to react before the alkali metal hydroxide, and the generated fluoroalcohol organic base can be inhibited from reacting in reverse. Specifically, typical but not limiting reaction temperatures are-5 ℃, -4 ℃, -3 ℃, -2 ℃, -1 ℃, 0 ℃, 1 ℃,2 ℃, 3 ℃, 4 ℃, 5 ℃, 6 ℃, 7 ℃, 8 ℃,9 ℃, 10 ℃.
In some embodiments, after obtaining the fluoroalcohol organic base, the reaction temperature is raised to 30-60 ℃ to promote bimolecular nucleophilic substitution reaction between the fluoroalcohol organic base and the p-toluenesulfonate, and the bimolecular nucleophilic substitution reaction time is preferably 3-8 h. Specifically, typical but not limiting reaction temperatures are 30 ℃, 35 ℃, 40 ℃, 45 ℃, 50 ℃, 55 ℃, 60 ℃; typical but not limiting reaction times are 3h, 4h, 5h, 6h, 7h, 8 h.
After bimolecular nucleophilic substitution reaction, because excessive p-toluenesulfonate ester may exist in the reaction system, in some embodiments, in order to remove the excessive p-toluenesulfonate ester, the excessive p-toluenesulfonate ester can be completely decomposed to generate a water-soluble salt by raising the temperature of the reaction system to 60-90 ℃ and reacting for 1-3 h. Specifically, typical but not limiting reaction temperatures are 60 ℃, 65 ℃, 70 ℃, 75 ℃, 80 ℃, 85 ℃, 90 ℃; typical but not limiting reaction times are 1h, 2h, 3 h.
Correspondingly, the embodiment of the invention also provides an inert electrolyte cosolvent, which comprises the fluorine-containing ether compound or the fluorine-containing ether compound prepared by the preparation method of the fluorine-containing ether compound.
The electrolyte provided by the embodiment of the invention comprises the inert electrolyte cosolvent, and because the fluorine-containing ether compound in the inert electrolyte cosolvent has higher oxidation-resistant potential, the oxidation reaction at the final charging stage can be avoided, and the high voltage stability of the electrolyte is improved; secondly, the fluorine-containing ether compound has higher fluorine content, so that the flammability of the electrolyte can be reduced, and the safety of the electrolyte can be improved; in addition, the high content of fluorine atoms can be decomposed on the surface of the lithium metal negative electrode to generate lithium fluoride, so that the lithium metal is stabilized, and the growth of lithium dendrites is inhibited.
In some embodiments, in order to improve the ionic conductivity and improve the cathode deposition quality, and enable the electrolysis process to reach a better state, the electrolyte provided by the embodiments of the present invention further includes an electrolyte and/or an additive in addition to the above fluorine-containing ether compound as a cosolvent.
Preferably, the electrolyte is selected from at least one of lithium hexafluorophosphate, lithium bistrifluoromethylsulfonyl imide, lithium bistrifluorosulfonimide, lithium tetrafluoroborate and lithium difluorooxalato borate, so as to ensure good ionic conductivity of the electrolyte; the concentration of the electrolyte is more preferably 0.5mol/L to 4 mol/L. Specifically, typical, but not limiting, electrolyte concentrations are 0.5mol/L, 1mol/L, 1.5mol/L, 2mol/L, 2.5mol/L, 3mol/L, 3.5mol/L, 4 mol/L.
Preferably, the additive is at least one of fluoroethylene carbonate (FEC), ethylene sulfate (DTD) and Vinylene Carbonate (VC) to promote the film forming stability of the negative electrode; the mass of the electrolyte accounts for 0.2-5% of the total mass of the electrolyte.
Correspondingly, the embodiment of the invention also provides a lithium secondary battery which comprises the electrolyte.
The lithium secondary battery provided by the embodiment of the invention comprises the electrolyte, so that the lithium secondary battery has more excellent high-voltage stability and safety; stable passageThe lithium metal is fixed, the growth of lithium dendrite is inhibited to slow down the attenuation of the battery capacity, the shuttle effect of irreversible loss of active substances and capacity caused by the fact that lithium polysulfide is dissolved in electrolyte and diffuses to a negative electrode is avoided by reducing the solubility of the lithium polysulfide in the electrolyte, and the cycle stability of the obtained lithium secondary battery is remarkably improved. Through analysis of a transverse flow charge-discharge test, the lithium copper half cell based on the electrolyte provided by the embodiment of the invention is at 1mA/cm2The current density is 1mAh/cm2The circulating 100-turn average coulombic efficiency under the condition of surface capacity is more than 99 percent; when NCM622 is used as a positive electrode active material, the capacity retention rate of 100 cycles under the condition of charge-discharge rate of 0.5C is more than 90%.
In some embodiments, the electrolyte provided by the embodiments of the present invention is particularly suitable for preparing lithium metal batteries, lithium ion batteries and lithium sulfur batteries because the fluorine-containing ether compound has the effects of stabilizing lithium metal, inhibiting the growth of lithium dendrites, and reducing the solubility of lithium polysulfide in the electrolyte.
In some embodiments, the positive active material of the lithium secondary battery provided by the embodiments of the present invention is preferably NCM111, NCM622, NCM532, NCM811, LiFePO4、LiCo2、LiMnO2Or LiNiMn; the negative active material is preferably at least one of lithium metal, graphite, and mesocarbon microbeads.
In order to make the above implementation details and operations of the present invention clearly understood by those skilled in the art and to make the advanced performances of the fluoroether compound, the preparation method thereof, the electrolyte and the lithium secondary battery of the embodiments of the present invention obviously manifest, the above technical solutions are illustrated by a plurality of examples below.
Example 1
A preparation method of a fluorine-containing ether compound comprises the following steps:
(1) dissolving 0.214mol of 2, 2-difluoroethanol (the molecular structural formula of which is shown in formula (i)) in 65mL of tetrahydrofuran, and dropwise adding 65mL of 6M NaOH solution under the ice bath condition to generate 2, 2-difluoroethanol sodium solution; dissolving 0.22mol of p-toluenesulfonyl chloride in 50mL of tetrahydrofuran, adding the solution into the 2, 2-difluoroethanol sodium solution under the conditions of ice bath and stirring, stirring and reacting for 1 hour under the condition of ice bath, heating to room temperature, continuing stirring to fully react for 1.5 hours, and then adding 170mL of NaOH solution (1M) to convert the excessive p-toluenesulfonyl chloride into water-soluble salt so as to be convenient for removal; then adding 200mL of diethyl ether for extraction, washing the mixture for three times by using ultrapure water, and removing the diethyl ether by decompression and spinning to obtain p-toluenesulfonic acid-2, 2-difluoroethyl ester;
(2) dissolving the p-toluenesulfonic acid-2, 2-difluoroethyl ester (0.2mol) obtained in the step (1) in N-methylpyrrolidone (50mL), and adding 2, 2-difluoroethanol (0.214mol) to obtain a solution; simultaneously preparing 45 wt% potassium hydroxide solution, and dripping potassium hydroxide solution (50mL) into the solution at 0 ℃ to convert 2, 2-difluoroethanol into potassium 2, 2-difluoroethoxide; after the dropwise addition, the temperature is raised to 50 ℃ for bimolecular nucleophilic substitution reaction for 5 hours, then the temperature is raised to 70 ℃ for reaction for 2 hours, so that excessive p-toluenesulfonic acid-2, 2-difluoroethyl ester is decomposed to generate water-soluble salt for removal, after the reaction is finished, the system is cooled to room temperature, ultrapure water is added, the product is extracted with diethyl ether for three times, the combined diethyl ether solution is washed with saturated saline solution for three times, and the diethyl ether is removed by reduced pressure rotary evaporation to obtain the crude product. Removing water from the crude product by using calcium hydride, and distilling at normal pressure to collect the final product fluorine-containing ether compound with the molecular structural formula shown in (I) at 125-130 ℃.
And (3) taking the final product obtained in the step (2) as a cosolvent, and adding the cosolvent into a 1M LiFSI solution (the solvent is ethylene glycol dimethyl ether), wherein the volume of the cosolvent is 0.5mL, and the dosage of the ethylene glycol dimethyl ether is 0.5mL, so as to obtain the electrolyte. The electrolyte is assembled into a lithium-copper half-cell, a lithium sheet is taken as a negative electrode, a copper foil is taken as a positive electrode, and a deposition/dissolution electrochemical test is carried out (the test method is referred to a literature Zheng J., Ji G, et al]Advanced Energy Materials,2019,9(16), for characterizing the growth of lithium dendrites during electrochemical cycling, the higher the coulombic efficiency of deposition/dissolution, the less the active lithium metal generates dead lithium during electrochemical process, i.e. lithium dendrites are not easily generated, and the better the reversibility of the lithium metal negative electrode is; the more cycles indicate that the electrolyte can support the long-term stable cycle of the lithium metal half-cell. TestingThe results are shown in FIG. 1, which shows that the concentration of the compound at 0.5mA/cm is shown in FIG. 12Current density, 1mAh/cm2The average coulombic efficiency of 100 cycles of circulation under the condition of surface capacity is more than 99 percent.
Example 2
A preparation method of a fluorine-containing ether compound comprises the following steps:
(1) dissolving 0.214mol of 2-fluoroethanol (the molecular structural formula of which is shown in formula (ii)) in 65mL of tetrahydrofuran, and dropwise adding 65mL of 6M NaOH solution under the ice bath condition to generate a 2-fluoroethanol sodium solution; dissolving 0.25mol of p-toluenesulfonyl chloride in 50mL of tetrahydrofuran, adding the solution into the 2-fluoroethanol sodium solution under the conditions of ice bath and stirring, stirring and reacting for 1.5 hours under the condition of ice bath, heating to room temperature, continuing stirring to fully react for 2 hours, and then adding 170mL of NaOH solution (1M) to convert the excessive p-toluenesulfonyl chloride into water-soluble salt so as to be convenient for removal; then adding 200mL of diethyl ether for extraction, washing the mixture for three times by using ultrapure water, and removing the diethyl ether by decompression and spinning to obtain p-toluenesulfonic acid-2-fluoroethyl ester;
(2) dissolving p-toluenesulfonic acid-2-fluoroethyl ester (0.2mol) obtained in the step (1) in N-methylpyrrolidone (50mL), and adding 2-fluoroethanol (0.214mol) to obtain a solution; simultaneously preparing 50 wt% of potassium hydroxide solution, and dripping potassium hydroxide solution (50mL) into the solution at 0 ℃ to convert 2-fluoroethanol into 2-fluoroethanol potassium; after the dropwise addition, the temperature is raised to 50 ℃ for bimolecular nucleophilic substitution reaction for 6 hours, then the temperature is raised to 70 ℃ for reaction for 1 hour, so that excessive p-toluenesulfonic acid-2-fluoroethyl ester is decomposed to generate water-soluble salt for removal, after the reaction is finished, the system is cooled to room temperature, ultrapure water is added, the product is extracted with ethyl ether for three times, the combined ethyl ether solution is washed with saturated saline solution for three times, and the ethyl ether is removed by reduced pressure rotary evaporation to obtain the crude product. Removing water from the crude product by using calcium hydride, and distilling at normal pressure to collect the final product fluorine-containing ether compound with the molecular structural formula shown in (II) at 110-115 ℃.
And (3) taking the final product obtained in the step (2) and ethylene glycol dimethyl ether as a solvent, and dissolving 1.2M LiFSI solution (the solvent is ethylene glycol dimethyl ether), wherein the dosage of the fluorine-containing ether compound is 0.6mL), and the dosage of the ethylene glycol dimethyl ether is 0.4mL, so as to obtain 1mL of electrolyte. Electrochemical tests were performed using LFP (lithium iron phosphate) as the positive electrode and a lithium sheet as the negative electrode (see documents Zheng J., Ji G, et al, high-Fluorinated Electrolytes for Li-S Batteries [ J ]. Advanced Energy Materials,2019,9 (16)), and the test results are shown in fig. 2, and fig. 2 shows that the capacity retention ratio of 100 cycles is greater than 90% under the condition of a current density of 0.5C in a battery cycle data diagram of LFP versus lithium sheet based on the electrolyte.
Example 3
A preparation method of a fluorine-containing ether compound comprises the following steps:
(1) dissolving 0.214mol of 3-fluoro-1-propanol (the molecular structural formula of which is shown in formula (iii)) in 65mL of tetrahydrofuran, and dropwise adding 65mL of 6M NaOH solution under the ice bath condition to generate 2-fluoroethanol sodium solution; dissolving 0.27mol of p-toluenesulfonyl chloride in 50mL of tetrahydrofuran, adding the solution into the 3-fluoro-1-sodium propoxide solution under the conditions of ice bath and stirring, stirring and reacting for 1 hour under the condition of ice bath, heating to room temperature, continuing stirring to fully react for 1.5 hours, and then adding 170mL of NaOH solution (1M) to convert the excessive p-toluenesulfonyl chloride into water-soluble salt so as to be convenient for removal; then adding 200mL of diethyl ether for extraction, washing the mixture for three times by using ultrapure water, and removing the diethyl ether by decompression and spinning to obtain p-toluenesulfonic acid-3-fluorine-1-propyl ester;
(2) dissolving the p-toluenesulfonic acid-3-fluoro-1-propyl ester (0.2mol) obtained in the step (1) in N-methylpyrrolidone (40mL), and adding 3-fluoro-1-propanol (0.214mol) to obtain a solution; simultaneously preparing 55 wt% of potassium hydroxide solution, and dripping potassium hydroxide solution (50mL) into the solution at 0 ℃ to convert the 3-fluoro-1-propanol into the 3-fluoro-1-propanol potassium; after the dropwise addition, the temperature is raised to 50 ℃ for bimolecular nucleophilic substitution reaction for 5.5 hours, then the temperature is raised to 70 ℃ for reaction for 1.5 hours, so that excessive p-toluenesulfonic acid-2-fluoroethyl ester is decomposed to generate water-soluble salt for removal, after the reaction is finished, the system is cooled to room temperature, ultrapure water is added, the product is extracted with diethyl ether for three times, the combined diethyl ether solution is washed with saturated saline solution for three times, and the diethyl ether is removed by reduced pressure rotary evaporation to obtain the crude product. Removing water from the crude product by using calcium hydride, and distilling at normal pressure to collect the final product fluorine-containing ether compound with the molecular structural formula shown in (III) at 115-120 ℃.
Adding the final product of the step (2) containing fluoroether compound as a cosolvent into 1M LiPF6In a solution (EC/DEC as solvent in a volume ratio of 3:7), wherein the volume of the cosolvent is 0.5mL, LiPF6The volume of the solution was 1mL, an electrolyte was obtained, a lithium copper half cell was assembled, and an electrochemical test was performed (see, for the method of the test, Zheng J., Ji G, et al, high-Fluorinated Electrolytes for Li-S Batteries [ J.]Advanced Energy Materials,2019,9(16), the test results are shown in fig. 3, the cell is at 1mA/cm2Current density, 1mAh/cm2The average coulombic efficiency of 100 cycles under the condition of surface capacity is more than 98 percent.
Example 4
A preparation method of a fluorine-containing ether compound comprises the following steps:
(1) dissolving 0.214mol of 2, 2-difluoroethanol (the molecular structural formula of which is shown in formula (i)) in 65mL of tetrahydrofuran, and dropwise adding 65mL of 6M NaOH solution under the ice bath condition to generate 2, 2-difluoroethanol sodium solution; dissolving 0.29mol of p-toluenesulfonyl chloride in 50mL of tetrahydrofuran, adding the solution into the 2, 2-difluoroethanol sodium solution under the conditions of ice bath and stirring, stirring and reacting for 1 hour under the condition of ice bath, heating to room temperature, continuing stirring to fully react for 1.5 hours, and then adding 170mL of NaOH solution (1M) to convert the excessive p-toluenesulfonyl chloride into water-soluble salt so as to be convenient for removal; then adding 200mL of diethyl ether for extraction, washing the mixture for three times by using ultrapure water, and removing the diethyl ether by decompression and spinning to obtain p-toluenesulfonic acid-2, 2-difluoroethanol ester;
(2) dissolving the p-toluenesulfonic acid-2, 2-difluoroethanol ester (0.2mol) obtained in the step (1) in N-methylpyrrolidone (40mL), and adding 2-fluoroethanol (the molecular structural formula of which is shown in a formula (ii), 0.214mol) to obtain a solution; simultaneously preparing 45 wt% of potassium hydroxide solution, and dripping potassium hydroxide solution (50mL) into the solution at the temperature of 0 ℃ to convert 2-fluoroethanol into 2-fluoroethanol potassium; after the dropwise addition, the temperature is raised to 50 ℃ for bimolecular nucleophilic substitution reaction for 5 hours, then the temperature is raised to 70 ℃ for reaction for 1.5 hours, so that the excessive p-toluenesulfonic acid-2, 2-difluoroethanol ester is decomposed to generate water-soluble salt for removal, after the reaction is finished, the system is cooled to room temperature, ultrapure water is added, the product is extracted with ether for three times, the combined ether solution is washed with saturated salt water for three times, and the ether is removed by reduced pressure rotary evaporation to obtain the crude product. Removing water from the crude product by using calcium hydride, and distilling at normal pressure to collect the final product fluorine-containing ether compound with the molecular structural formula of (IV) at the temperature of 120-122 ℃.
And (3) taking the final product of the step (2) as a cosolvent, adding a 1M LiTFSI solution (the solvent is ethylene glycol dimethyl ether), wherein the volume of the fluorine-containing ether compound is 0.5mL, the volume of the ethylene glycol dimethyl ether is 0.5mL, adding 5 wt% of VC (vinylene carbonate) to obtain an electrolyte, assembling the lithium-sulfur battery, and carrying out an electrochemical test (the test method is referred to the literature Zheng J., Ji G, et al, high-Fluorinated Electrolytes for Li-S Batteries [ J ]. Advanced Energy Materials,2019 (16)). The test results are shown in fig. 4. The capacity of the lithium-sulfur battery is maintained at 91% after 100 cycles under the condition of 0.5C current density.
Example 5
A preparation method of a fluorine-containing ether compound comprises the following steps:
(1) dissolving 0.214mol of 2, 2-difluoroethanol (the molecular structural formula of which is shown in formula (i)) in 65mL of tetrahydrofuran, and dropwise adding 65mL of 6M NaOH solution under the ice bath condition to generate 2, 2-difluoroethanol sodium solution; dissolving 0.26mol of p-toluenesulfonyl chloride in 50mL of tetrahydrofuran, adding the solution into the 2, 2-difluoroethanol sodium solution under the conditions of ice bath and stirring, stirring and reacting for 1 hour under the condition of ice bath, heating to room temperature, continuing stirring to fully react for 1.5 hours, and then adding 170mL of NaOH solution (1M) to convert the excessive p-toluenesulfonyl chloride into water-soluble salt so as to be convenient for removal; then adding 200mL of diethyl ether for extraction, washing the mixture for three times by using ultrapure water, and removing the diethyl ether by decompression and spinning to obtain p-toluenesulfonic acid-2, 2-difluoroethyl ester;
(2) dissolving the p-toluenesulfonic acid-2, 2-difluoroethyl ester (0.2mol) obtained in the step (1) in N-methylpyrrolidone (40mL), and adding 3-fluoro-1-propanol (the molecular structural formula is shown in formula (iii), and the mol is 0.214mol) to obtain a solution; simultaneously preparing 45 wt% of potassium hydroxide solution, and dripping potassium hydroxide solution (50mL) into the solution at 0 ℃ to convert the 3-fluoro-1-propanol into the 3-fluoro-1-propanol potassium; after the dropwise addition, the temperature is raised to 50 ℃ for bimolecular nucleophilic substitution reaction for 6 hours, then the temperature is raised to 70 ℃ for reaction for 2 hours, so that excessive p-toluenesulfonic acid-2, 2-difluoroethyl ester is decomposed to generate water-soluble salt for removal, after the reaction is finished, the system is cooled to room temperature, ultrapure water is added, the product is extracted with diethyl ether for three times, the combined diethyl ether solution is washed with saturated saline solution for three times, and the diethyl ether is removed by reduced pressure rotary evaporation to obtain the crude product. Removing water from the crude product by using calcium hydride, and distilling at normal pressure to collect the final product fluorine-containing ether compound with the molecular structural formula shown in (V) at the temperature of 123-125 ℃.
And (3) taking the final product obtained in the step (2) and ethylene glycol dimethyl ether as solvents, dissolving LiTFSI in the solvents to enable the concentration of lithium salt to be 4M, and adding 2.5 wt% of DTD (vinyl sulfate), wherein the volume of the fluorine-containing ether compound is 0.5mL, and the volume of the ethylene glycol dimethyl ether is 0.5mL, so as to obtain the electrolyte. The electrolyte is assembled into a lithium-copper half-cell, a lithium sheet is taken as a negative electrode, a copper foil is taken as a positive electrode, and a deposition/dissolution electrochemical test is carried out (the test method is referred to a literature Zheng J., Ji G, et al]Advanced Energy Materials,2019,9(16), the test results are shown in fig. 5, the lithium copper half cell is at 1mA/cm2Current density, 1mAh/cm2The average coulombic efficiency of 100 cycles circulating under the condition of surface capacity is more than 90 percent.
Example 6
A preparation method of a fluorine-containing ether compound comprises the following steps:
(1) dissolving 0.214mol of 2-fluoroethanol (the molecular structural formula of which is shown in formula (ii)) in 65mL of tetrahydrofuran, and dropwise adding 65mL of 6M NaOH solution under the ice bath condition to generate a 2-fluoroethanol sodium solution; dissolving 0.3mol of p-toluenesulfonyl chloride in 50mL of tetrahydrofuran, adding the solution into the 2-fluoroethanol sodium solution under the conditions of ice bath and stirring, stirring and reacting for 1.5 hours under the condition of ice bath, heating to room temperature, continuing stirring to fully react for 2 hours, and then adding 170mL of NaOH solution (1M) to convert the excessive p-toluenesulfonyl chloride into water-soluble salt so as to be convenient for removal; then adding 200mL of diethyl ether for extraction, washing the mixture for three times by using ultrapure water, and removing the diethyl ether by decompression and spinning to obtain p-toluenesulfonic acid-2-fluoroethyl ester;
(2) dissolving the p-toluenesulfonic acid-2-fluoroethyl ester (0.2mol) obtained in the step (1) in N-methylpyrrolidone (40mL), and adding 3-fluoro-1-propanol (the molecular structural formula is shown in formula (iii), and the mol is 0.214mol) to obtain a solution; simultaneously preparing 45 wt% of potassium hydroxide solution, and dripping potassium hydroxide solution (50mL) into the solution at 0 ℃ to convert the 3-fluoro-1-propanol into the 3-fluoro-1-propanol potassium; after the dropwise addition, the temperature is raised to 60 ℃ for bimolecular nucleophilic substitution reaction for 5 hours, then the temperature is raised to 70 ℃ for reaction for 2 hours, so that excessive p-toluenesulfonic acid-2-fluoroethyl ester is decomposed to generate water-soluble salt for removal, after the reaction is finished, the system is cooled to room temperature, ultrapure water is added, the product is extracted with diethyl ether for three times, the combined diethyl ether solution is washed with saturated saline solution for three times, and the diethyl ether is removed through reduced pressure rotary evaporation, so that the crude product is obtained. Removing water from the crude product by using calcium hydride, and distilling at normal pressure to collect the final product fluorine-containing ether compound with the molecular structural formula shown in (VI), wherein the temperature of 128-135 ℃ is 128-.
And (3) taking the final product of the step (2) and the fluoroethylene glycol dimethyl ether as main solvents, dissolving LiTFSI in the obtained main solvent to ensure that the concentration of lithium salt is 4M, and adding 0.5 wt% of FEC (fluoroethylene carbonate), wherein the volume of the fluoroethylene ether compound is 0.5mL, and the volume of the ethylene glycol dimethyl ether is 0.5mL to obtain the electrolyte. The electrolyte is assembled into a lithium metal battery, a lithium sheet is used as a negative electrode, NCM622 is used as a positive electrode, constant-current charge and discharge electrochemical tests are carried out (the test method is shown in the literature Zheng J., Ji G, et al, high-Fluorinated Electrolytes for Li-S Batteries [ J ]. Advanced Energy Materials,2019 and 9 (16)), and the test result is shown in FIG. 6, and the capacity retention rate is more than 85% after 100 cycles of circulation under the condition of 0.2C.
Comparative example
To dissolve 1M, LiPF6The electrochemical test was performed using the EC/DEC (volume ratio: 3:7) of (1) as an electrolyte, LFP (lithium iron phosphate) as a positive electrode, and a lithium plate as a negative electrode (the method of the test is described in Zheng J., Ji G, e)t al.High-Fluorinated Electrolytes for Li-S Batteries[J]Advanced Energy Materials,2019,9(16), the test results are shown in fig. 7. As can be seen from fig. 7, the capacity retention rate was 76.5% at a current density of 0.5C for 100 cycles of the battery based on this electrolyte.
The above examples are only preferred embodiments of the present invention, which are intended to be illustrative and not limiting, and those skilled in the art should understand that they can make various changes, substitutions and alterations without departing from the spirit and scope of the invention.
Claims (10)
1. A fluorine-containing ether electrolyte cosolvent used for a lithium metal/lithium ion/lithium sulfur battery is characterized by comprising a fluorine-containing ether compound; the structural formula of the fluorine-containing ether compound is more than one of the following formulas (I) to (VI):
2. the fluoroether-containing electrolyte cosolvent for a lithium metal/lithium ion/lithium sulfur battery according to claim 1, wherein said fluoroether-containing compound is prepared by:
(1) mixing p-toluenesulfonyl chloride, fluorine alcohol and alkali metal hydroxide to generate p-toluenesulfonate from the p-toluenesulfonyl chloride and the fluorine alcohol;
(2) and mixing the p-toluenesulfonate, the fluoroalcohol and the alkali metal hydroxide for treatment, reacting the fluoroalcohol with the alkali metal hydroxide to generate fluoroalcohol organic base, and carrying out bimolecular nucleophilic substitution reaction on the fluoroalcohol organic base and the p-toluenesulfonate to generate the fluorine-containing ether compound.
3. The fluoroether-containing electrolyte cosolvent for a lithium metal/lithium ion/lithium sulfur battery according to claim 2, wherein said alkali metal hydroxide of step (1) is one or more of sodium hydroxide and potassium hydroxide; the molar ratio of the p-toluenesulfonyl chloride to the fluoroalcohol to the alkali metal hydroxide is 1:1:1 to 1:1: 3.
4. The fluoroether-containing electrolyte cosolvent for a lithium metal/lithium ion/lithium sulfur battery according to claim 2, wherein the mixing treatment temperature of the step (1) is-5 ℃ to 10 ℃.
5. The fluoroether-containing electrolyte cosolvent for a lithium metal/lithium ion/lithium sulfur battery according to claim 2, wherein the molar ratio of the p-toluenesulfonate, the fluoroalcohol and the alkali metal hydroxide in step (2) is 1:1:1 to 1:1: 3.
6. The fluoroether-containing electrolyte cosolvent for a lithium metal/lithium ion/lithium sulfur battery according to claim 2, wherein the temperature of the mixing treatment of the step (2) is-5 ℃ to 10 ℃; the temperature of bimolecular nucleophilic substitution reaction in the step (2) is 30-60 ℃; the time of bimolecular nucleophilic substitution reaction is 3h-8 h.
7. An electrolyte comprising the fluoroether-based electrolyte co-solvent for a lithium metal/lithium ion/lithium sulfur battery according to any one of claims 1 to 6.
8. The electrolyte of claim 7, further comprising one or more of an electrolyte and an additive; the electrolyte is at least one of lithium hexafluorophosphate, lithium bis (trifluoromethyl) sulfonyl imide and lithium bis (fluoro) sulfonyl imide; the concentration of the electrolyte is 0.5-4 mol/L; the additive is at least one of fluoroethylene carbonate, ethylene sulfate and vinylene carbonate; the mass of the additive accounts for 0.2-5% of the total mass of the electrolyte.
9. The electrolyte of claim 7, further comprising an electrolyte and an additive; the electrolyte is at least one of lithium hexafluorophosphate, lithium bis (trifluoromethyl) sulfonyl imide and lithium bis (fluoro) sulfonyl imide; the concentration of the electrolyte is 0.5-4 mol/L; the additive is at least one of fluoroethylene carbonate, ethylene sulfate and vinylene carbonate; the mass of the additive accounts for 0.2-5% of the total mass of the electrolyte.
10. A lithium secondary battery comprising the electrolyte according to any one of claims 8 to 9.
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