CN113410516B - Organic silicon electrolyte and preparation method and application thereof - Google Patents
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Abstract
The invention provides an organic silicon electrolyte and a preparation method and application thereof, wherein the organic silicon electrolyte is prepared by reacting all components according to mass percent to obtain a prepolymer, and then crosslinking and curing the prepolymer; the prepolymer comprises the following components in percentage by mass: 2-70% of an organic silicon electrolyte matrix, 5-30% of high dielectric constant organic silicon, 10-40% of lithium salt, 1-20% of an organic silicon electrolyte matrix modified inorganic filler and 0.1-5% of an initiator. The invention synthesizes a polymer monomer material with lithium-conducting capacity and inorganic particle surface modification capacity, and can be solidified into solid electrolyte, the polymer monomer material has good dispersing capacity through coupling modification with inorganic particles, a special interface channel for conducting lithium ions is constructed to improve the electrolyte performance, and the safety of the battery is enhanced through a solidified structure.
Description
Technical Field
The invention relates to the technical field of lithium battery materials, in particular to an organic silicon electrolyte and a preparation method and application thereof.
Background
Currently, commercial lithium ion battery electrolytes are mainly dissolved with lithium hexafluorophosphate (LiPF)6) The mixed solvent system of the cyclic carbonate and the chain carbonate has the characteristics of good lithium salt solubility, high ionic conductivity, capability of forming a stable solid electrolyte interface film (SEI film) on the surface of a graphite cathode and the like. However, the materials have the defects of easy leakage, easy volatilization, inflammability, insufficient oxidation resistance and the like, limit the further improvement of the energy density of the lithium ion battery, and are easy to cause safety accidents.
With the higher and higher requirements of the market on the energy density and the safety of the lithium ion battery, the research and development of a high-voltage and high-safety electrolyte matched with the lithium ion battery becomes an urgent task for the development of electrolyte materials.
Patent application No. CN201610055337.1 provides a novel polymer electrolyte for lithium ion batteries and a preparation method thereof. The patent with the application number of CN201010607369.0 provides an organic silicon amine electrolyte containing polyether chains and the application thereof in a lithium battery, the synthesized organic silicon amine electrolyte containing polyether chains has good electrochemical performance, but the electrolytes have poor mechanical property, unstable size performance and certain liquid leakage risk. The patent with the application number of CN201610055337.1 provides a novel polymer electrolyte for a lithium ion battery and a preparation method thereof, and the polymer electrolyte with end groups crosslinked is prepared by taking a silicon methoxy end-capped polyether oligomer as a matrix polymer and taking a lithium borate salt as a lithium source and catalyzing the in-situ crosslinking of the matrix polymer. The patent with the application number of CN201710159748.X provides a polymer electrolyte which is formed by crosslinking and curing a terminated polyether oligomer with end silane as a prepolymer, a conductive lithium salt as a lithium source, an organic solvent as a plasticizer and a tin salt as a catalyst, and application of the polymer electrolyte in a lithium ion polymer battery.
Disclosure of Invention
The invention aims to provide an organic silicon electrolyte and a preparation method thereof, which solve the problems of poor electrode contact, larger interface impedance, low conductivity, easy crystallization, narrow applicable temperature range, non-ideal mechanical property and the like.
Another object of the present invention is to provide the use of silicone electrolytes in lithium ion batteries.
The purpose of the invention is realized by the following technical scheme:
an organic silicon electrolyte, which is prepared by crosslinking and curing a prepolymer; the prepolymer comprises the following components in percentage by mass: 2-70% of an organic silicon electrolyte matrix, 5-30% of high dielectric constant organic silicon, 10-40% of lithium salt, 1-20% of an organic silicon electrolyte matrix modified inorganic filler and 0.1-5% of an initiator.
Further, the chemical general formula of the organic silicon electrolyte matrix is as follows:
the long-chain polyether-free silicon methoxyl-terminated polyether oligomer or silane-terminated polyether oligomer is used as an electrolyte matrix, the long-chain polyether-free silicon methoxyl-terminated polyether oligomer has limited lithium salt dissolving capacity, a long-distance lithium conducting channel cannot be formed, the lithium conducting capacity of the electrolyte is low, the silane-terminated polyether oligomer is used as the electrolyte matrix, polymerization and solidification can be carried out only through double bonds, inorganic substances cannot be coupled, and the combination with the electrode material and the surface of an inorganic filler is poor. The long-chain polyether chain segment can interact with lithium ions, promote dissociation of the lithium ions, construct a conduction channel and improve lithium ion conduction. And the existence of the long-chain polyether chain segment enables the electrolyte to have certain flexibility while keeping certain mechanical strength, thereby being beneficial to the long-cycle stability of the battery.
Further, the organic silicon electrolyte matrix modified inorganic filler is an organic silicon electrolyte matrix modified nano material, and the high dielectric constant organic silicon is cyclic carbonate modified organic silicon.
The organosilicon material has the characteristics of excellent safety, oxidation resistance, thermal stability, flame retardance, film forming property and the like, and becomes one of the directions for developing novel electrolytes by replacing electrolyte. In addition, the unique hydrosilylation reaction of the organic silicon material enables the organic silicon material to have the advantages of easy functionalization modification through reaction, hydrolysis reaction of the alkoxy silicon ester and coupling with the inorganic material to form an organic-inorganic composite system.
Further, the cyclic carbonate modified silicone is a silicone material containing the following functional group R:
R。
further, preferably, the cyclic carbonate-modified silicone is preferably 2- (4- (1, 3-dioxolan-2-one) ethyl pentamethyl disiloxane RCH2Si(CH3)2OSi(CH3)34- (2-trimethylsilylethyl) -1, 3-dioxolan-2-one RCH2CH2Si(CH3)24- (2-trimethylsiloxysilyldimethylethyl) -1, 3-dioxolan-2-one RC2H4Si(CH3)2OSi(CH3)3One or more of them.
Further, the lithium salt includes one or more of LiPF6, LiTFSI, LiFSI, liddob, LiBOB.
Further, the initiator comprises azobisisobutyronitrile or dibenzoyl peroxide.
Based on the same inventive concept, the invention provides a preparation method of the organic silicon electrolyte, which comprises the following steps:
s1, preparing an organic silicon electrolyte matrix: adding a catalyst into an allyl-terminated polyvinyl alcohol material and a material containing a silicon-hydrogen bond and a Si-OR bond to perform hydrosilylation reaction with a solvent, adding methyl propionyl chloride and organic amine, and performing esterification reaction in the solvent to obtain an organic silicon electrolyte matrix, wherein the chemical reaction process is as follows:
s2, preparing the organic silicon electrolyte matrix modified inorganic filler: ultrasonically dispersing the nano filler and the organic silicon electrolyte matrix in an organic reagent, heating, cooling, centrifugally separating, washing with a solvent, and drying to obtain the organic silicon electrolyte matrix modified inorganic filler;
s3, preparing an organic silicon electrolyte: and (3) uniformly stirring the organic silicon electrolyte matrix and the organic silicon electrolyte matrix modified inorganic filler respectively prepared in the steps S1 and S2 with high dielectric constant organic silicon, lithium salt and an initiator to obtain a prepolymer, and crosslinking and curing the prepolymer to obtain the organic silicon electrolyte.
The application of organosilicon materials to lithium ion batteries with their unique physicochemical properties is receiving continuous attention, and functionalized organosilicon compounds used as electrolyte solvents or additives can exhibit excellent safety, oxidation resistance, thermal stability, flame retardancy, film-forming properties, etc., and polymer electrolytes formed by organosilicon with polymer matrix also have application in lithium ion batteries.
Further, the nano filler described in step S2 includes: of silicon oxide, aluminum oxide, titanium oxide
One or more of them.
Further, in step S1, the hydrosilylation catalyst includes one or more of a catalyst in the form of a card and a catalyst in the form of a solution of chloroplatinic acid, and the solvent includes one or more of toluene, benzene, and tetrahydrofuran; the organic amine in the esterification reaction comprises one or more of urea, triethylamine and pyridine, and the solvent comprises one or more of acetone, tetrahydrofuran, toluene, dichloromethane and trichloromethane.
Further, the molar ratio of the allyl-terminated polyvinyl alcohol material to the material containing silicon-hydrogen bonds and Si — OR bonds in step S1 is 1: 0.5 to 3; the molar ratio of the methyl propionyl chloride to the organic amine material is 0.5-3: 1, the mass content of the catalyst is 0.5-1%.
Further, the molar ratio of the allyl-terminated polyvinyl alcohol material, the silicon-containing hydrogen bond and the Si — OR bond in the step S1 is 1: 1.2, the molar ratio of the methylpropanoyl chloride to the organic amine material is 1.2: 1.
further, in the step S2, the heating temperature is 60-120 ℃, and the mass ratio of the nano filler to the organic silicon electrolyte matrix is 50: 1-200: 1;
further, in the step S3, the heating temperature for crosslinking, curing and heating is 45-120 ℃, and the heating time is 3-48 hours.
Based on the same inventive concept, the invention provides a lithium ion battery, which comprises the organic silicon electrolyte.
The invention has the beneficial effects that:
firstly, designing a polyether modified organic silicon electrolyte matrix, introducing a methacrylic acid group, alkoxy silicon ester and a polyether chain segment through hydrosilylation and esterification, wherein the methacrylic acid group has high free radical polymerization capability and can quickly solidify an electrolyte prepolymer from a liquid state to a solid state; the segmented polyether chain segment can form coordination with lithium ions to promote the conduction capability of the lithium ions; the silicon alkoxide can be coupled with the surface of an inorganic substance to form an inorganic-organic compound. Compared with the traditional short-chain silane coupling agent, the polyether chain segment carried by the electrolyte matrix can reduce the possibility of agglomeration of nanoparticles through surface active groups while wrapping the inorganic nano filler, and improve the dispersion of inorganic particles in the electrolyte.
During the formation of the electrolyte prepolymer, organic silicon electrolyte matrix modified inorganic nanoparticles and cyclic carbonate modified organic silicon materials are added. Compared with the unmodified inorganic material, the modified inorganic material improves the dispersibility, is beneficial to constructing a special lithium ion conduction channel interface and improves the lithium ion conduction performance. Thirdly, performing; the cyclic carbonate has a high dielectric constant, can promote the dissociation of lithium salt, has the effect of forming a film on the surface of an electrode, can improve the dissociation of the lithium salt and the conductivity by introducing the cyclic carbonate modified organosilicon material, and can form a good interface film on the surface of the electrode to improve the cycle performance of the battery.
Based on the method, the polymer monomer material with lithium conducting capacity and inorganic particle surface modification capacity is synthesized, the polymer monomer material can be solidified into solid electrolyte, the polymer monomer material has good dispersing capacity through coupling modification with inorganic particles, a special interface channel for conducting lithium ions is constructed to improve the electrolyte performance, and the safety of the battery is enhanced through a solidified structure.
Drawings
FIG. 1 is an AC impedance spectrum of the battery prepared in example 1;
FIG. 2 is a plot of the AC impedance of the cell prepared in example 2;
fig. 3 is a plot of the ac impedance of the cell prepared in example 3.
Detailed Description
The present invention is further illustrated by the following specific examples in the specification, which are not intended to limit the invention in any way. Reagents, methods and apparatus used in the present invention are conventional in the art unless otherwise indicated. Unless otherwise specified, all the raw materials and equipment used in this example were those conventionally available in the art.
Example 1
The embodiment comprises the following specific steps:
s1, preparing an organic silicon electrolyte matrix: in a 250mL dry four-necked flask with a thermometer, condenser and stirrer through which argon was simultaneously introduced, 0.25mol of allyl polyethylene glycol (molecular weight: 400) and 0.3mol of HSi (OC)2H5)3Adding into a bottle, stirring, and heating to 60 deg.CoC, dripping 0.4mL of chloroplatinic acid solution, continuing to react for 2h, cooling to room temperature, discharging, and distilling under reduced pressure to remove unreacted HSi (OC)2H5)3And obtaining a hydrosilylation product. 0.1mol of hydrosilylation product, 0.1mol of triethylamine and 50mL of tetrahydrofuran are mixed and then added into a flask with a thermometer, a condenser, a stirrer and a constant pressure funnel, 0.12mol of methacryloyl chloride is dissolved in 30mL of tetrahydrofuran and poured into the constant pressure funnel, the temperature is controlled at 50 ℃ by stirring, the mixture is added into the flask for 0.5 hour, and the stirring reaction is continued for 3.5 hours. Filtering the obtained product to remove salt, taking the filtrate, and removing the solvent and unreacted materials under reduced pressure at 50 ℃ to obtain the organic silicon electrolyte matrix.
S2, preparing the organic silicon electrolyte matrix modified inorganic filler: 0.05g of the organosilicon electrolyte matrix obtained in S1 and 10g of silica were added to 100ml of toluene, dispersed for 30 minutes by ultrasonic (300W), transferred to a flask equipped with a reflux condenser and a stirrer, and heated to 110 deg.CoAnd C, heating and refluxing for 2h, cooling, performing centrifugal separation, washing with absolute ethyl alcohol, and drying to obtain the modified nano silicon dioxide material.
S3, taking 0.6g of product organic silicon electrolyte matrix prepared by S1, 0.01g of modified nano-silica material prepared by S2, 0.29g of 2- (4- (1, 3-dioxolane-2-one) ethyl pentamethyl disiloxane and LiPF60.1g of azobisisobutyronitrile and 0.0001g of azobisisobutyronitrile were uniformly stirred to obtain a prepolymer material, 60oC, heating for 24h, crosslinking and curing to obtain the organic silicon electrolyte, assembling the organic silicon electrolyte into a button cell, and obtaining a solid-state battery, wherein an alternating current impedance spectrum is shown in figure 1.
Example 2
The embodiment comprises the following specific steps:
s1, preparing an organic silicon electrolyte matrix: the stirrer is simultaneously communicated with the thermometer, the condenser and the stirrerInto a 250mL dry four-necked flask charged with argon, 0.25mol of allyl polyethylene glycol (molecular weight: 600) and 0.3mol of HSi (OCH)3)3Adding into a bottle, stirring, and heating to 60 deg.CoC, dripping 0.4mL of chloroplatinic acid solution, continuing to react for 2h, cooling to room temperature, discharging, and distilling under reduced pressure to remove unreacted HSi (OCH)3)3To obtain the hydrosilylation product. 0.1mol of hydrosilylation product, 0.1mol of triethylamine and 50mL of tetrahydrofuran are mixed and then added into a flask with a thermometer, a condenser, a stirrer and a constant pressure funnel, 0.12mol of methacryloyl chloride is dissolved in 30mL of tetrahydrofuran and poured into the constant pressure funnel, the temperature is controlled at 50 ℃ by stirring, the mixture is added into the flask for 0.5 hour, and the stirring reaction is continued for 3.5 hours. Filtering the obtained product to remove salt, taking the filtrate, and removing the solvent and unreacted materials under reduced pressure at 50 ℃ to obtain the organic silicon electrolyte matrix.
S2, preparing the organic silicon electrolyte matrix modified inorganic filler: 0.05g of the organic silicon electrolyte matrix obtained in S1 and 10g of alumina were added to 100ml of tetrahydrofuran, and the mixture was ultrasonically (300W) dispersed for 30 minutes and transferred to a flask equipped with a reflux condenser and a stirrer for 60 minutesoAnd C, heating and refluxing for 6 hours, cooling, performing centrifugal separation, washing with absolute ethyl alcohol, and drying to obtain the modified nano-silica material.
S3, taking 0.7g of product organic silicon electrolyte matrix prepared by S1, 0.05g of modified nano aluminum oxide material prepared by S2, 0.05g of 4- (2-trimethylsilylethyl) -1, 3-dioxolane-2-one, 0.2g of LiTFSI and 0.0002g of azobisisobutyronitrile, stirring uniformly to obtain a prepolymer material, 60oHeating for 24h, crosslinking and curing to obtain the organic silicon electrolyte, assembling the organic silicon electrolyte into a button cell, and obtaining a solid-state battery, wherein the alternating current impedance spectrum of the solid-state battery is shown in figure 2.
Example 3
The embodiment comprises the following specific steps:
s1, preparing an organic silicon electrolyte matrix: in a 250mL dry four-necked flask having a thermometer, a condenser and a stirrer through which argon was simultaneously introduced, 0.25mol of allyl polyethylene glycol (molecular weight: 600) and 0.3mol of HSi (OCH)3)3Adding into a bottle, stirring and heating to60oC, dripping 0.4mL of chloroplatinic acid solution, continuously reacting for 2h, cooling to room temperature, discharging, and distilling under reduced pressure to remove unreacted HSi (OCH)3)3And obtaining a hydrosilylation product. 0.1mol of hydrosilylation product, 0.1mol of triethylamine and 50mL of tetrahydrofuran are mixed and then added into a flask with a thermometer, a condenser, a stirrer and a constant pressure funnel, 0.12mol of methacryloyl chloride is dissolved in 30mL of tetrahydrofuran and poured into the constant pressure funnel, the temperature is controlled at 50 ℃ by stirring, the mixture is added into the flask for 0.5 hour, and the stirring reaction is continued for 3.5 hours. And filtering the obtained product to remove salt, taking the filtrate, and removing the solvent and unreacted materials under reduced pressure at 50 ℃ to obtain the organic silicon electrolyte matrix.
S2, preparing the organic silicon electrolyte matrix modified inorganic filler: 0.05g of the organic silicon electrolyte matrix obtained in S1 and 10g of titanium oxide were added to 100ml of tetrahydrofuran, and the mixture was ultrasonically (300W) dispersed for 30 minutes and transferred to a flask equipped with a reflux condenser and a stirrer for 60 minutesoAnd C, heating and refluxing for 6h, cooling, performing centrifugal separation, washing with absolute ethyl alcohol, and drying to obtain the modified nano silicon dioxide material.
S3, taking 0.2g of product organic silicon electrolyte matrix prepared by S1, 0.2g of modified nano titanium oxide prepared by S2, 0.3g of 4- (2-trimethylsiloxy dimethylsilyl ethyl) -1, 3-dioxolane-2-one, 0.3g of LiDFOB and 0.0002g of azodiisobutyronitrile, uniformly stirring to obtain a prepolymer material, 60oC, heating for 24h, and crosslinking and curing to obtain the solid electrolyte. And assembling the button cell to obtain a solid-state battery, wherein the alternating current impedance spectrum of the solid-state battery is shown in figure 3.
Fig. 1 to 3 are graphs of ac impedance of the solid-state batteries according to embodiments 1 to 3, respectively, and it can be seen from the graphs that the impedance values of the solid-state batteries are small. The conduction resistance of electrons and ions is small, and the transmission performance of electrons in the material is better.
It should be understood that the above-mentioned examples are only preferred examples for clearly illustrating the technical solutions of the present invention, and are not intended to limit the embodiments of the present invention. Other variations and modifications will be apparent to persons skilled in the art in light of the above description. And are neither required nor exhaustive of all embodiments. The invention can be applied to various fields of medical equipment, such as a medical equipment, a medical equipment and a medical equipment. Any modification, equivalent replacement, and improvement made within the spirit and principle of the present invention should be included in the protection scope of the claims of the present invention.
Claims (7)
1. An organic silicon electrolyte is characterized in that the organic silicon electrolyte is prepared by crosslinking and curing a prepolymer; the prepolymer comprises the following components in percentage by mass: 2-70% of an organic silicon electrolyte matrix, 5-30% of high-dielectric-constant organic silicon, 10-40% of lithium salt, 1-20% of an organic silicon electrolyte matrix modified inorganic filler and 0.1-5% of an initiator;
the preparation method of the organic silicon electrolyte comprises the following steps:
s1, preparation of an organic silicon electrolyte matrix: allyl-terminated polyethylene glycol materials with silicon-containing hydrogen bonds and Si-OR1Adding a catalyst into a material of the bond to perform hydrosilylation reaction with a solvent, adding methacryloyl chloride and organic amine, and performing esterification reaction in the solvent to obtain an organic silicon electrolyte matrix;
the chemical general formula of the organic silicon electrolyte matrix is as follows:
S2, preparing the organic silicon electrolyte matrix modified inorganic filler: ultrasonically dispersing the nano filler and the organic silicon electrolyte matrix into an organic reagent, heating, cooling, centrifugally separating, washing with a solvent, and drying to obtain the organic silicon electrolyte matrix modified inorganic filler;
s3, preparation of organic silicon electrolyte: uniformly stirring the organic silicon electrolyte matrix and the organic silicon electrolyte matrix modified inorganic filler respectively prepared in the steps S1 and S2 with high dielectric constant organic silicon, lithium salt and an initiator to obtain a prepolymer, and crosslinking and curing the prepolymer to obtain the organic silicon electrolyte;
the high dielectric constant organic silicon is cyclic carbonate modified organic silicon and comprises the following functional group R2：
R2。
2. The silicone electrolyte of claim 1, wherein the cyclic carbonate-modified silicone is 2- (4- (1, 3-dioxolan-2-one) ethyl pentamethyldisiloxane R2CH2Si(CH3)2OSi(CH3)34- (2-trimethylsilylethyl) -1, 3-dioxolan-2-one R2CH2CH2Si(CH3)24- (2-trimethylsilyloxydimethylsilyl) -1, 3-dioxolan-2-one R2C2H4Si(CH3)2OSi(CH3)3One or more of them.
3. The silicone electrolyte of claim 1, wherein the lithium salt comprises LiPF6One or more of LiTFSI, LiFSI, liddob, LiBOB; the initiator comprises azobisisobutyronitrile or dibenzoyl peroxide.
4. The silicone electrolyte of claim 1, wherein the nanofiller of step S2 comprises: one or more of silicon oxide, aluminum oxide and titanium oxide.
5. The silicone electrolyte of claim 1, wherein the hydrosilylation catalyst in step S1 comprises one or more of a catalyst selected from the group consisting of a catalyst in the form of a catalyst card and a catalyst in the form of a solution of chloroplatinic acid, and the solvent comprises toluene, benzene, and tetrahydrofuranOne or more of (a); the organic amine in the esterification reaction comprises one or more of urea, triethylamine and pyridine, and the solvent comprises one or more of acetone, tetrahydrofuran, toluene, dichloromethane and trichloromethane; step S1 reaction of allyl-terminated polyethylene glycol with Si-OR containing hydrogen bond1The material molar ratio of the bond is 1: 0.5 to 3; the mol ratio of the methacryloyl chloride to the organic amine material is 0.5-3: 1, the mass content of the catalyst is 0.5-1%.
6. The organic silicon electrolyte as claimed in claim 1, wherein the heating temperature in step S2 is 60-120 ℃, and the mass ratio of the nano filler to the organic silicon electrolyte matrix is 50: 1-200: 1;
and S3, the heating temperature of the cross-linking curing is 45-120 ℃, and the heating time is 3-48 h.
7. Use of the silicone electrolyte according to any one of claims 1 to 6 in a lithium ion battery.
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