CN111416147A - Composite solid polymer electrolyte and preparation method thereof - Google Patents
Composite solid polymer electrolyte and preparation method thereof Download PDFInfo
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- CN111416147A CN111416147A CN202010152212.7A CN202010152212A CN111416147A CN 111416147 A CN111416147 A CN 111416147A CN 202010152212 A CN202010152212 A CN 202010152212A CN 111416147 A CN111416147 A CN 111416147A
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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
- H01M10/0565—Polymeric materials, e.g. gel-type or solid-type
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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
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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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
- H01M2300/00—Electrolytes
- H01M2300/0017—Non-aqueous electrolytes
- H01M2300/0065—Solid electrolytes
- H01M2300/0082—Organic polymers
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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
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Abstract
The invention discloses a solid polymer electrolyte doped with modified nano-filler and a preparation method thereof, belonging to the technical field of solid polymer electrolyte materials. The novel solid polymer electrolyte doped with the modified nano filler is prepared by mixing the silicon dioxide nano particles modified by the cyclic carbonate, lithium salt, polyoxyethylene and a solvent capable of dissolving the polyoxyethylene, and drying to form a film. The preparation method comprises the following steps: preparing the silicon dioxide nano particles modified by the cyclic carbonate, preparing electrolyte mixed liquid and preparing an electrolyte film. The preparation method has the advantages of simple preparation process, high efficiency and low production cost, and the obtained solid polymer electrolyte of the lithium ion battery has good ionic conductivity and mechanical strength, excellent safety performance and very high market prospect.
Description
The technical field is as follows:
the invention belongs to the technical field of solid polymer electrolyte materials, and particularly relates to a solid polymer electrolyte doped with modified nano-filler and a preparation method thereof.
Background art:
the electrolyte material of the lithium ion battery has excellent ion conduction performance and simultaneously has the advantages ofL iPF widely used in commercial Li-ion batteries at present6The carbonate-based electrolyte has high ionic conductivity and good wetting performance, but has the defects of easy combustion, easy volatilization, insufficient oxidation resistance and the like, and further improvement of the safety and energy density of the lithium ion battery is severely restricted. In contrast, a solid electrolyte material contains no or only a small amount of liquid components, and is expected to fundamentally solve the safety problem of batteries.
Organic-inorganic composite solid electrolytes are one type of electrolyte formed by incorporating inorganic particles into a conventional polymer electrolyte. The polymer-based electrolyte can compensate the volume change of the electrode in the charge and discharge process through elastic and plastic deformation; and the inorganic filler is introduced into the polymer electrolyte, so that the crystallization of a polymer substrate and the interaction of the recombined polymer and lithium ions can be inhibited, and the ion conduction performance, the interface performance and the mechanical strength of the electrolyte can be effectively improved. However, the compatibility between the inorganic filler and the polymer matrix needs to be improved, and the filler is easily agglomerated in the polymer matrix, thereby affecting the performance of the electrolyte. Related patent technology CN03136183.3 discloses a composite solid polymer electrolyte prepared from a polymer matrix, lithium salt and modified or unmodified inorganic nanoparticles, wherein the inorganic nanoparticles are modified by silane coupling agents (KH550, KH560, KH570, KH792) containing epoxy group, amino group and acrylate group respectively; CN03119735 discloses a composite solid polymer electrolyte prepared from a polymer matrix, lithium salt and modified inorganic nanoparticles, wherein the surface groups of the inorganic silica nanoparticles can be hydroxyl, trimethylsilyl, or polydimethylsilane; CN201710059631 discloses a mercapto group-containing silane coupling agent mixed with a polymer substrate to form a membrane, and then the mercapto group is oxidized to sulfonic group, and then in-situ polymerized and lithiated to prepare a lithium salt-containing composite solid polymer electrolyte membrane; CN201810072837.5 discloses a composite gel polymer electrolyte membrane with ionic liquid modified nano-silica as filler; CN201910269774.7 discloses a self-healing polymer electrolyte prepared by compounding UPy functionalized silica nanoparticles with a copolymer of UpyMA and PEGMA with a self-healing function. The above patents all use inorganic silica nanoparticles as the filler of the composite solid polymer electrolyte, and by introducing the inorganic silica nanoparticles or the inorganic nanoparticles with surface functionalization modification, the inorganic silica nanoparticles have better dispersibility in the polymer matrix, and can also endow the composite solid polymer electrolyte with more functional characteristics.
L iPF with high ionic conductivity and good wetting property widely used in commercial lithium ion batteries6The carbon carbonate-based electrolyte has the defects of easy combustion, easy volatilization, insufficient oxidation resistance and the like, but cyclic carbonate groups have high dielectric constant, good solubility to lithium salts and the characteristic of contributing to ionic conductivity, and the electrolyte utilizing the functionalization of the cyclic carbonate groups is still a hot spot developed by the current commercial electrolyte, such as fluoro-carbonate, vinyl functionalized carbonate, ionic liquid functionalized carbonate, sulfonic functionalized carbonate, long-chain alkyl functionalized carbonate and organic silicon functionalized carbonate.
The invention content is as follows:
the invention aims to provide a composite solid polymer electrolyte doped with modified silica nano-filler and a preparation method thereof, wherein the cyclic carbonate modified silica nano-filler has better dispersibility, better compatibility with polyethylene oxide and better dissociation capability to lithium salt; the composite solid electrolyte material exhibits good mechanical properties and ionic conductivity. The preparation method has simple process and low cost, and is beneficial to large-scale production.
In order to achieve the purpose, the invention adopts the technical scheme that:
a composite solid polymer electrolyte consisting of: modified nano silicon dioxide particles, lithium salt and polyethylene oxide with lithium conducting capacity.
The mass fraction of the cyclic carbonate modified nano silicon dioxide particles in the electrolyte is 1-50%, the mass fraction of the lithium salt in the electrolyte is 15-50%, and the mass fraction of the polyethylene oxide with the lithium conducting capacity in the electrolyte is 30-80%.
Further, the cyclic carbonate modified nano silica particles are prepared according to a method comprising the following steps:
step 1: dispersing nano silicon dioxide particles into a solvent, wherein the nano silicon dioxide accounts for 0.1-10% of the solvent by mass percent, and the nano silicon dioxide particles are uniformly dispersed by ultrasonic;
step 2: under the condition of stirring, adding a silane coupling agent modified by the cyclic carbonate shown in the formula (1) according to the mass ratio of the nano silicon dioxide particles to the silane coupling agent modified by the cyclic carbonate of 10:1-1: 10:
wherein R is1Selected from the following structural units: - (CH)2)n- (n-1-3), or-CH2OCH2CH2CH2-；R2，R3，R4Selected from alkoxy or halogen substituent groups;
and step 3: reacting for 0.5-12 hours at the temperature of 30-120 ℃, and drying after centrifugal separation and absolute ethyl alcohol washing to obtain the silicon dioxide nano-particles modified by the cyclic carbonate.
Further, in step 1, the nano-silica is hydrophilic nano-silica, particles of whichThe diameter is 7-40nm, and the specific surface area is 380m2/g。
Further, in the step 1, the solvent is one or more of methanol, ethanol, tetrahydrofuran, toluene, xylene and dichloromethane.
Further, in step 2, the preparation method of the cyclic carbonate modified silane coupling agent comprises the following steps: prepared by a cycloaddition reaction of a silane coupling agent containing an oxirane group (KH560) with carbon dioxide in the presence of a quaternary ammonium salt, or a carbonate containing a double bond (vinyl ethylene carbonate) with a silane in the presence of chloroplatinic acid by a hydrosilation reaction.
Further, in step 3, the conditions for the centrifugal separation were 8000-.
The lithium salt is lithium perchlorate (L iClO)4) Lithium hexafluoroarsenate (L iAsF)6) Lithium tetrafluoroborate (L iBF)4) Lithium hexafluorophosphate (L iPF)6) Lithium bistrifluoromethylsulfonyl imide (L iTFSI), lithium bistrifluoromethylsulfonyl imide (L iFSI), lithium triflate (L iCF)3SO3) One or more of lithium bis (oxalato) borate (L iBOB), lithium difluoro (oxalato) borate (L iODFB) and lithium chloride (L iCl).
In order to achieve the above object, the present invention provides a method for preparing a composite solid polymer electrolyte, comprising the steps of:
step 1: dissolving polyoxyethylene in a solvent to prepare a polymer solution with the mass percentage concentration of 2-20%, and adding lithium salt;
step 2: dispersing the silicon dioxide nano particles modified by the cyclic carbonate into the polymer solution obtained in the step 1, dispersing for 0.5-24 hours at the temperature of 20-90 ℃, casting to form a film after uniform dispersion, and volatilizing a solvent to obtain a polymer film, namely the lithium ion battery composite solid electrolyte film;
the solvent in step 1 and step 2 comprises acetonitrile, acetone, N-Dimethylformamide (DMF), N-methylpyrrolidone (NMP) or water.
After the composite solid polymer electrolyte is prepared into a membrane, the thickness of the membrane is between 50 and 200 um.
The composite solid polymer electrolyte is characterized in that the ionic conductivity reaches 8.9 × 10-6S/cm, the conductivity of the blank composite solid electrolyte material doped with the silica nanoparticles without the modification of the cyclic carbonate under the same condition (3.5 × 10)-7S/cm) by an order of magnitude.
The method is simple to operate, high in safety and suitable for continuous large-scale production of the composite solid polymer electrolyte. The solid polymer electrolyte prepared by the invention has high ionic conductivity, wide electrochemical stability window and good compatibility with electrodes, and is beneficial to improving the safety performance of the lithium ion battery. The solid polymer electrolyte membrane prepared by the electrolyte has high mechanical strength and good chemical stability, and is also suitable for the design and production of flexible batteries.
The invention has the following beneficial effects:
the modified silica nano filler provided by the invention has the advantages that the surface of the modified silica nano filler is functionalized with the cyclic carbonate group, and the dissociation of lithium salt can be further promoted by introducing the carbonate functional group, so that the improvement of the ionic conductivity of the solid polymer electrolyte is facilitated.
The modified silica nano filler can effectively solve the problems of easy agglomeration of nano particles and poor compatibility with a polymer substrate by functionalizing the cyclic carbonate groups on the surface of the modified silica nano filler, and is beneficial to uniform dispersion of the filler in a matrix.
After the polymer membrane prepared by the invention is assembled into a battery, electrochemical tests show that the solid polymer electrolyte has good particle conductivity and electrochemical stability: the room-temperature particle conductivity is one order of magnitude higher than that of the composite polymer electrolyte without the modification of the cyclic carbonate, the electrochemical stability window can reach more than 5V, and the practical application requirements of the lithium ion battery can be met.
Description of the drawings:
fig. 1 is an infrared contrast spectrum of the cyclic carbonate-modified silica nanoparticles prepared in example 1 of the present invention.
Fig. 2 is a thermogram of the cyclic carbonate-modified silica nanoparticles prepared in example 1 of the present invention.
Fig. 3 is a graph comparing ion conductivity of silica nanoparticle-doped composite solid polymer electrolyte materials with/without cyclic carbonate modification in examples 3 and 7 (blank) of the present invention.
The specific implementation mode is as follows:
the following is a further description of the invention and is not intended to be limiting. After reading this disclosure, modifications of various equivalent forms of the present invention by those skilled in the art will fall within the scope of the appended claims of this application.
Example 1
The preparation method of the cyclic carbonate modified nano silicon dioxide particles comprises the following steps of dispersing 0.5g of nano silicon dioxide particles into a 50m L toluene solvent, uniformly dispersing by ultrasonic, adding 0.2g of cyclic carbonate modified silane coupling agent (4-ethyl-1, 3-dioxolane-2-ketone is substituted by monomethyldichlorosilane) under the stirring condition, reacting for 0.5 hour at the temperature of 120 ℃, centrifuging under the condition of 10000r/min, washing for 3 times by ethanol, and drying at the temperature of 80 ℃ to obtain the cyclic carbonate modified silicon dioxide nano particles.
Example 2
The preparation method of the cyclic carbonate modified nano silica particles comprises the following steps of dispersing 0.5g of nano silica particles into 20m L ethanol solvent, uniformly dispersing by ultrasonic, adding 5g of cyclic carbonate modified silane coupling agent (trimethoxy silane replaces 4- [ (propoxy) methyl ] -1, 3-dioxolane-2-ketone) under the stirring condition, reacting for 12 hours at the temperature of 30 ℃, centrifuging under the condition of 10000r/min, washing for 3 times by using ethanol, and drying at the temperature of 80 ℃ to obtain the cyclic carbonate modified silica nano particles.
Example 3
Polyethylene oxide (PEO), the cyclic carbonate-modified silica nanoparticles prepared in example 1, and lithium perchlorate (L iClO) in a mass ratio of 3:1:1 were placed in an argon glove box4) Fully dissolving in acetonitrile, stirring for 24 hr to obtain uniform viscous solution, and introducing electrolyte mixtureThe membrane is poured on a polytetrafluoroethylene plate, the solvent is evaporated, and then the solid polymer electrolyte membrane doped with the nano filler is dried in a vacuum drying oven for 48 hours at the temperature of 80 ℃, the thickness of the prepared solid polymer electrolyte membrane is about 160 mu m, the electrochemical window is more than 5.2V, and the ionic conductivity is 8.9 × 10 under the temperature condition of 30 DEG C-6S/cm。
Example 4
Fully dissolving polyethylene oxide (PEO), the cyclic carbonate modified silica nanoparticles prepared in example 2 and lithium bis (oxalato) borate (L iBOB) in acetonitrile in a mass ratio of 5:4:4 in an argon glove box, stirring for 24 hours to obtain a uniform viscous solution, then pouring an electrolyte mixed solution on a polytetrafluoroethylene plate to evaporate the solvent, and drying in a vacuum drying box at 80 ℃ for 48 hours, wherein the thickness of the prepared solid polymer electrolyte membrane doped with the nanofiller is about 100 mu m, the electrochemical window is more than 5.0V, and the ionic conductivity is 8.3 × 10 under the temperature condition of 30 DEG C-6S/cm。
Example 5
Polyethylene oxide (PEO), the cyclic carbonate-modified silica nanoparticles prepared in example 1, and lithium hexafluorophosphate (L iPF) in a mass ratio of 3:5:4 were placed in an argon glove box6) Fully dissolving in acetonitrile, stirring for 24 hours to obtain uniform viscous solution, then pouring the electrolyte mixed solution on a polytetrafluoroethylene plate, evaporating the solvent, and then drying in a vacuum drying oven at 80 ℃ for 48 hours, wherein the thickness of the prepared solid polymer electrolyte membrane doped with the nano filler is about 70um, the electrochemical window is more than 5.0V, and the ionic conductivity is 7.8 × 10 under the temperature condition of 30 DEG C-6S/cm。
Example 6
Fully dissolving polyethylene oxide (PEO), the cyclic carbonate modified silicon dioxide nano-particles prepared in example 1 and lithium bistrifluoromethylsulfonyl imide (L iTFSI) in distilled water in a mass ratio of 2:2:3, stirring for 24 hours to obtain a uniform viscous solution, then pouring an electrolyte mixed solution on a polytetrafluoroethylene plate to form a film, evaporating the solvent, and drying at 80 ℃ for 48 hours in a vacuum drying oven to prepare the solid polymer electrolyte film doped with the nano fillerThe thickness is about 120um, the electrochemical window is more than 5.0V, and the ionic conductivity is 9.7 × 10 under the temperature condition of 30 DEG C-6S/cm。
Example 7
Polyethylene oxide (PEO), silica nanoparticles, lithium perchlorate (L iClO) in a mass ratio of 3:1:1 in an argon glove box4) Fully dissolving in acetonitrile, stirring for 24 hours to obtain uniform viscous solution, then pouring the electrolyte mixed solution on a polytetrafluoroethylene plate, evaporating the solvent, and then drying in a vacuum drying oven at 80 ℃ for 48 hours, wherein the thickness of the prepared solid polymer electrolyte membrane doped with the nano filler is about 160 mu m, the electrochemical window is more than 5.0V, and the ionic conductivity is 3.5 × 10 under the temperature condition of 30 DEG C-7S/cm。
Claims (5)
1. A composite solid polymer electrolyte consisting of: modified nano silicon dioxide particles, lithium salt and polyethylene oxide with lithium conducting capacity; the method is characterized in that: the composite solid polymer electrolyte takes nano silicon dioxide particles modified by cyclic carbonate as a filler, and the nano particles modified by the cyclic carbonate are beneficial to improving the dispersibility and compatibility of the nano silicon dioxide particles in polyethylene oxide and the interaction between the nano silicon dioxide particles and lithium salt; the mass fraction of the cyclic carbonate modified nano silicon dioxide particles in the electrolyte is 1-50%, the mass fraction of the lithium salt in the electrolyte is 15-50%, and the mass fraction of the polyethylene oxide with the lithium conducting capacity in the electrolyte is 30-80%.
2. The composite solid polymer electrolyte of claim 1, wherein: the cyclic carbonate modified nano silicon dioxide particles are prepared according to a method comprising the following steps:
step 1: dispersing nano silicon dioxide particles into a solvent, wherein the nano silicon dioxide accounts for 0.1-10% of the solvent by mass percent, and the nano silicon dioxide particles are uniformly dispersed by ultrasonic;
step 2: under the condition of stirring, adding a silane coupling agent modified by the cyclic carbonate shown in the formula (1) according to the mass ratio of the nano silicon dioxide particles to the silane coupling agent modified by the cyclic carbonate of 10:1-1: 10:
wherein R is1Selected from the following structural units: - (CH)2)n- (n-1-3), or-CH2OCH2CH2CH2-；R2，R3，R4Selected from alkoxy or halogen substituent groups;
and step 3: reacting for 0.5-12 hours at the temperature of 30-120 ℃, and drying after centrifugal separation and absolute ethyl alcohol washing to obtain the silicon dioxide nano-particles modified by the cyclic carbonate.
3. The composite solid polymer electrolyte according to claim 1, wherein the lithium salt is lithium perchlorate (L iClO)4) Lithium hexafluoroarsenate (L iAsF)6) Lithium tetrafluoroborate (L iBF)4) Lithium hexafluorophosphate (L iPF)6) Lithium bistrifluoromethylsulfonyl imide (L iTFSI), lithium bistrifluoromethylsulfonyl imide (L iFSI), lithium triflate (L iCF)3SO3) One or more of lithium bis (oxalato) borate (L iBOB), lithium difluoro (oxalato) borate (L iODFB) and lithium chloride (L iCl).
4. A preparation method of a composite solid polymer electrolyte is characterized by comprising the following steps:
step 1: dissolving polyoxyethylene in a solvent to prepare a polymer solution with the mass percentage concentration of 2-20%, and adding lithium salt;
step 2: and (2) dispersing the silicon dioxide nano particles modified by the cyclic carbonate into the polymer solution obtained in the step (1), dispersing for 0.5-24 hours at the temperature of 20-90 ℃, casting to form a film after uniform dispersion, and volatilizing the solvent to obtain a polymer film, namely the lithium ion battery composite solid electrolyte film.
5. The method of claim 4, wherein the solvent in the steps 1 and 2 comprises acetonitrile, acetone, N-Dimethylformamide (DMF), N-methylpyrrolidone (NMP) or water.
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| CN114335710A (en) * | 2021-12-17 | 2022-04-12 | 西安交通大学 | Preparation method and application of double-modified solid electrolyte membrane |
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