CN111416146B - Modified nano silicon dioxide and preparation method and application thereof - Google Patents

Modified nano silicon dioxide and preparation method and application thereof Download PDF

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CN111416146B
CN111416146B CN202010151620.0A CN202010151620A CN111416146B CN 111416146 B CN111416146 B CN 111416146B CN 202010151620 A CN202010151620 A CN 202010151620A CN 111416146 B CN111416146 B CN 111416146B
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silicon dioxide
lithium
electrolyte
bridged
particles
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CN111416146A (en
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汪靖伦
韩冲宇
孙天霷
何延昭
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Hunan University of Science and Technology
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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
    • 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
    • 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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    • Y02E60/10—Energy storage using batteries

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Abstract

The invention discloses modified nano silicon dioxide and a preparation method thereof. The modified nano silicon dioxide is prepared by the following method: the amino functionalized silica nanoparticle reacts with dianhydride compound to obtain the pyromellitic acid diimide bridged silica nanoparticle. The modified nano silicon dioxide provided by the invention and the preparation method and application thereof have the following advantages: 1. the preparation method adopts the efficient and simple amidation reaction to synthesize the pyromellitic acid diimide-bridge silica nanoparticle, and has simple operation and low requirement on equipment. 2. The pyromellitic acid diimide bridged silicon dioxide nano particles prepared by the method have better compatibility in the polymer, and the composite solid polymer electrolyte prepared by the method has better ionic conductivity.

Description

Modified nano silicon dioxide and preparation method and application thereof
Technical field:
the invention belongs to the technical field of solid polymer electrolyte materials, and particularly relates to a solid polymer electrolyte doped with modified nanofiller and a preparation method thereof.
The background technology is as follows:
the lithium ion battery electrolyte material is a material system with excellent ion conductivity and functional characteristics such as interface performance, electrochemical stability, thermal stability, safety, mechanical performance and the like. Currently, liPF widely used in commercial lithium ion batteries 6 The carbonate-based electrolyte has the defects of easy combustion, easy volatilization, insufficient oxidation resistance and the like, and severely restricts the further improvement of the safety and the energy density of the lithium ion battery, although the carbonate-based electrolyte has high ionic conductivity and good infiltration performance. In contrast, solid electrolyte materials have no or only a small amount of liquid components, and are expected to fundamentally solve the safety problem of batteries.
The organic-inorganic composite solid electrolyte is a type of electrolyte formed by introducing inorganic particles into a conventional polymer electrolyte. The polymer-based electrolyte can compensate for volume changes of the electrode during charge and discharge by elastic and plastic deformation; the inorganic filler is introduced into the polymer electrolyte, so that crystallization of the polymer substrate and interaction between the recombinant polymer and lithium ions can be inhibited, and the ion conduction performance, interface performance and mechanical strength of the electrolyte are effectively improved. However, the compatibility between the inorganic filler and the polymer matrix is to be improved, and the filler is easy to agglomerate in the polymer matrix, so that the performance of the electrolyte is affected. The related patent technology has CN03136183.3 disclosed 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 adopting silane coupling agents (KH 550, KH560, KH570, KH 792) containing amino groups, epoxy groups and acrylate groups; 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, polydimethylsilane; CN201710059631 discloses that the mercapto silane coupling agent is mixed with the polymer substrate to form a film, then the mercapto group is oxidized into a sulfonic acid group, and then in-situ polymerized and lithiated to prepare a lithium salt-containing composite solid polymer electrolyte film; CN201810072837.5 discloses a composite gel polymer electrolyte membrane with ionic liquid modified nano silica as filler; CN201910269774.7 discloses that the self-healing polymer electrolyte is prepared by compounding UPy functionalized silica nanoparticles with UpyMA and PEGMA copolymers having self-healing function. The inorganic silica nanoparticles are used as the composite solid polymer electrolyte filler, and the inorganic silica nanoparticles or the inorganic nanoparticles with surface functionalization modification are introduced, so that the inorganic silica nanoparticles have better dispersibility in a polymer matrix, and can endow the composite solid polymer electrolyte with more functional characteristics.
The polymer prepared by reacting diamine compounds with dianhydride monomers is used as a binder material and shows excellent electrochemical characteristics with a lithium ion battery (CN 201410591508.3) or a lithium sulfur battery (CN 201510422483.9). Firstly, preparing amino-functionalized nano silicon dioxide by reacting a commercialized amino-functionalized silane coupling agent with nano silicon dioxide particles, then preparing a pyromellitic acid diimide bridged silicon dioxide nano particle with a three-dimensional structure by reacting with dianhydride monomers, and preparing a solid electrolyte material by compounding with polyethylene oxide and lithium salt; the pyromellitic acid diimide bridged silicon dioxide nano particles are helpful for improving the salt dissolving capacity, the dispersibility and the compatibility of the materials in polyethylene oxide polymers, so as to develop the composite solid electrolyte material with high ion conductivity and excellent mechanical property.
The invention comprises the following steps:
the invention aims to provide a composite solid polymer electrolyte doped with modified silica nano filler and a preparation method thereof, wherein the silica nano filler bridged by pyromellitic acid diimide has better dispersibility, better compatibility with polyethylene oxide and better dissociation capability to lithium salt; the composite solid electrolyte material has better ionic conductivity and mechanical property. The preparation method has simple process and low cost, and is beneficial to mass production.
In order to achieve the above purpose, the invention adopts the following technical scheme:
a composite solid polymer electrolyte comprises the following components: the lithium ion battery comprises pyromellitic acid diimide bridged silicon dioxide nano particles, lithium salt and polyethylene oxide with lithium conducting capability.
The mass fraction of the pyromellitic acid diimide bridged silicon dioxide nano particles in the electrolyte is 1-30%, the mass fraction of the lithium salt in the electrolyte is 15-50%, and the mass fraction of the polyethylene oxide with lithium conducting capability in the electrolyte is 30-80%.
Further, the pyromellitic acid diimide-bridged silica nanoparticles are prepared according to a method comprising the steps of:
step 1: dispersing nano silicon dioxide particles into a solvent, wherein the nano silicon dioxide accounts for 0.1-10% of the mass of the solvent, and adding an amino-functionalized silane coupling agent to prepare amino-functionalized silicon dioxide nano particles;
step 2: adding pyromellitic dianhydride into the reaction liquid, reacting for 0.5-12 hours at the temperature of 60-120 ℃ according to the mass ratio of the amino-functionalized silica nanoparticles to the pyromellitic dianhydride of 10:1-1:10, and drying after centrifugal separation and absolute ethanol washing to obtain the pyromellitic dianhydride bridged silica nanoparticles.
Further, in the step 1, the nano silica is hydrophilic nano silica with a particle diameter of 7-40nm and a specific surface area of 380m 2 /g。
Further, in step 1, the commercial amino-containing silane coupling agent is: gamma-aminopropyl trimethoxysilane, gamma-aminopropyl triethoxysilane, N-2-aminoethyl-gamma-aminopropyl trimethoxysilane, gamma-diethylenetriamine propyl methyl dimethoxy silane, polyaminoalkyl triethoxysilane.
Further, in step 1, the solvent is one or more of methanol, ethanol, tetrahydrofuran, toluene, xylene and methylene dichloride.
Further, in step 2, the conditions for the centrifugal separation are 8000-14000r/min.
The lithium salt is lithium perchlorate (LiClO) 4 ) Lithium hexafluoroarsenate (LiAsF) 6 ) Lithium tetrafluoroborate (LiBF) 4 ) Lithium hexafluorophosphate (LiPF) 6 ) Lithium bis (trifluoromethylsulfonyl) imide (LiTFSI), lithium bis (fluorosulfonyl) imide (LiFSI), lithium trifluoromethylsulfonate (LiCF) 3 SO 3 ) One or more of lithium bisoxalato borate (LiBOB), lithium difluorooxalato borate (LiODFB) and lithium chloride (LiCl).
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: polyethylene oxide is dissolved in a solvent to prepare a polymer solution with the mass percent concentration of 2% -20%, and lithium salt is added;
step 2: dispersing the pyromellitic acid diimide bridged silicon dioxide nano particles into the polymer solution obtained in the step 1, dispersing for 0.5-24 hours at 20-90 ℃, uniformly dispersing, and then casting to form a film, wherein the polymer film is obtained after the solvent volatilizes, namely the lithium ion battery composite solid electrolyte film;
the solvent in the step 1 and the step 2 comprises acetonitrile, acetone, N-Dimethylformamide (DMF), N-methylpyrrolidone (NMP) or water.
After the composite solid polymer electrolyte is prepared into a film, the thickness of the film is 50-200 mu m.
The composite solid polymer electrolyte is characterized in that the ionic conductivity is 1.9 multiplied by 10 at the temperature of 30 DEG C -5 S/cm。
The invention has simple operation and high safety, and is suitable for continuous mass production of composite solid polymer electrolyte. The solid polymer electrolyte prepared by the invention has high ionic conductivity, wide electrochemical stability window and good compatibility with the electrode, 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 disclosed by the invention can further promote the dissociation of lithium salt through the bridge connection of pyromellitic acid diimide, and is beneficial to the improvement of the ionic conductivity of the solid polymer electrolyte.
The modified silica nano filler disclosed by the invention can effectively solve the problems of easy agglomeration of nano particles and poor compatibility with a polymer substrate by bridge connection of pyromellitic acid diimide, and is favorable for uniform dispersion of the filler in a matrix.
After the polymer film prepared by the invention is assembled into a battery, electrochemical tests show that the solid polymer electrolyte has good ionic conductivity, is higher than the composite polymer electrolyte doped with the non-modified silica nano particles by two orders of magnitude, and can meet the practical application requirements of lithium ion batteries.
Description of the drawings:
FIG. 1 is an infrared contrast spectrum of the pyromellitic acid diimide-bridged silica nanoparticles prepared in example 1 of the present invention.
FIG. 2 is a thermogravimetric plot of the pyromellitic acid diimide bridged silica nanoparticles prepared in example 1 of the present invention.
Fig. 3 is an ion conductivity diagram of a composite solid polymer electrolyte material doped with pyromellitic acid diimide-bridged silica nanoparticles in examples 3, 7 (blank) of the present invention.
The specific embodiment is as follows:
the following is a further illustration of the invention and is not a limitation of the invention. After reading the present invention, those skilled in the art will recognize that modifications of various equivalent forms of the present invention are within the scope of what is defined in the claims appended hereto.
Example 1
The pyromellitic acid diimide bridged silica nanoparticles were prepared as follows: 0.5g of nano silicon dioxide particles are dispersed into 50mL of toluene solvent, and ultrasonic dispersion is uniform: under the condition of stirring, adding 1.0g of gamma-aminopropyl trimethoxysilane, reacting for 0.5 hours at the temperature of 120 ℃, then adding 1.0g of pyromellitic dianhydride, reacting for 6 hours at the temperature of 120 ℃, centrifuging at 10000r/min after the reaction, washing for 3 times with ethanol, and drying at 80 ℃ to obtain the pyromellitic dianhydride bridged silicon dioxide nano particles.
Example 2
The pyromellitic acid diimide bridged silica nanoparticles were prepared as follows: dispersing 0.5g of nano silicon dioxide particles into 20mL of ethanol solvent, and uniformly dispersing by ultrasonic: adding 2.0g N-2-aminoethyl-gamma-aminopropyl trimethoxysilane under stirring, reacting for 12 hours at 30 ℃, adding 4.0g pyromellitic dianhydride, reacting for 12 hours at 80 ℃, centrifuging at 10000r/min after the reaction, washing for 3 times with ethanol, and drying at 80 ℃ to obtain the pyromellitic dianhydride bridged silicon dioxide nano particles.
Example 3
Polyoxy with mass ratio of 3:1:1 in argon glove boxEthylene Oxide (PEO), and the nanoparticles of pyromellitic acid diimide-bridged silica prepared in example 1, lithium perchlorate (LiClO) 4 ) Fully dissolved in acetonitrile, stirred for 24 hours to obtain a uniform viscous solution, then the electrolyte mixture is poured on a polytetrafluoroethylene plate to evaporate the solvent, and then dried in a vacuum drying oven at 80 ℃ for 48 hours. The prepared solid polymer electrolyte membrane doped with nano-filler has the thickness of about 160um, the electrochemical window of more than 5.3V and the ionic conductivity of 1.9X10 at 30 DEG C -5 S/cm。
Example 4
Polyethylene oxide (PEO), the pyromellitic acid diimide-bridged silica nanoparticles prepared in example 2, and lithium bisoxalato borate (LiBOB) were sufficiently dissolved in acetonitrile in an argon glove box in a mass ratio of 5:4:4, and a uniform viscous solution was obtained after stirring for 24 hours, and then the electrolyte mixed solution was prepared by casting a film on a polytetrafluoroethylene plate, evaporating the solvent, and then drying in a vacuum drying oven at 80℃for 48 hours. The thickness of the prepared solid polymer electrolyte membrane doped with nano-filler is about 100um, the electrochemical window is larger than 5.0V, and the ionic conductivity is 5.3 multiplied by 10 at 30 DEG C -5 S/cm。
Example 5
Polyethylene oxide (PEO), the pyromellitic diimide-bridged silica nanoparticles prepared in example 1, lithium hexafluorophosphate (LiPF) were mixed in a mass ratio of 3:5:4 in an argon glove box 6 ) Fully dissolved in acetonitrile, stirred for 24 hours to obtain a uniform viscous solution, then the electrolyte mixture is poured on a polytetrafluoroethylene plate to evaporate the solvent, and then dried in a vacuum drying oven at 80 ℃ for 48 hours. The prepared solid polymer electrolyte membrane doped with nano-filler has the thickness of about 70um, the electrochemical window of more than 5.1V and the ionic conductivity of 3.8X10 at 30 DEG C -5 S/cm。
Example 6
Polyethylene oxide (PEO) with a mass ratio of 2:2:3, the pyromellitic acid diimide-bridged silica nanoparticles prepared in example 1, lithium bis (trifluoromethyl) sulfonyl imide (LiTFSI)) Fully dissolved in distilled water, stirred for 24 hours to obtain a uniform viscous solution, then the electrolyte mixture is poured on a polytetrafluoroethylene plate to evaporate the solvent, and then dried in a vacuum drying oven at 80 ℃ for 48 hours. The prepared solid polymer electrolyte membrane doped with nano-filler has the thickness of about 120um, the electrochemical window of more than 5.0V and the ionic conductivity of 5.7X10 at 30 DEG C -5 S/cm。
Example 7
Polyethylene oxide (PEO), silica nanoparticles, lithium perchlorate (LiClO) in a mass ratio of 3:1:1 in an argon glove box 4 ) Fully dissolved in acetonitrile, stirred for 24 hours to obtain a uniform viscous solution, then the electrolyte mixture is poured on a polytetrafluoroethylene plate to evaporate the solvent, and then dried in a vacuum drying oven at 80 ℃ for 48 hours. The prepared solid polymer electrolyte membrane doped with nano-filler has a thickness of about 160um, an electrochemical window of more than 5.0V and an ionic conductivity of 3.5X10 at 30 DEG C -7 S/cm。

Claims (5)

1. The modified nano silica particle doped composite solid polymer electrolyte comprises the following components: modified nano silicon dioxide particles, lithium salt and polyethylene oxide; the method is characterized in that: the composite solid polymer electrolyte takes the silicon dioxide nano particles bridged by the pyromellitic acid diimide as a filler, and the modified silicon dioxide nano particles are beneficial to improving the dispersibility of the silicon dioxide nano particles in polyethylene oxide and the interaction of the silicon dioxide nano particles with lithium salt; the mass fraction of the pyromellitic acid diimide bridged silicon dioxide nano particles in the electrolyte is 1-30%, the mass fraction of the lithium salt in the electrolyte is 15-50%, and the mass fraction of the polyethylene oxide in the electrolyte is 30-80%.
2. The composite solid polymer electrolyte of claim 1, wherein: the pyromellitic acid diimide bridged silica nanoparticle is prepared according to a method comprising the steps of:
step 1: dispersing nano silicon dioxide particles into a solvent, wherein the nano silicon dioxide accounts for 0.1-10% of the mass of the solvent, and adding an amino-functionalized silane coupling agent to prepare amino-functionalized silicon dioxide nano particles;
step 2: adding pyromellitic dianhydride into the amino-functionalized silica reaction solution obtained in the step 1, wherein the mass ratio of the amino-functionalized silica nanoparticles to the pyromellitic dianhydride is 10:1-1:10, and the mixture is 60: o C-120 o and C, reacting for 0.5-12 hours at the temperature, and drying after centrifugal separation and absolute ethyl alcohol washing to obtain the pyromellitic acid diimide bridged silicon dioxide nano particles.
3. The composite solid polymer electrolyte of claim 1, wherein: the lithium salt is lithium perchlorate (LiClO) 4 ) Lithium hexafluoroarsenate (LiAsF) 6 ) Lithium tetrafluoroborate (LiBF) 4 ) Lithium hexafluorophosphate (LiPF) 6 ) Lithium bis (trifluoromethylsulfonyl) imide (LiTFSI), lithium bis (fluorosulfonyl) imide (LiFSI), lithium trifluoromethylsulfonate (LiCF) 3 SO 3 ) One or more of lithium bisoxalato borate (LiBOB), lithium difluorooxalato borate (LiODFB) and lithium chloride (LiCl).
4. The preparation method of the composite solid polymer electrolyte is characterized by comprising the following steps of:
step 1: polyethylene oxide is dissolved in a solvent to prepare a polymer solution with the mass percent concentration of 2% -20%, and lithium salt is added;
step 2: dispersing the nano-particles of the silicon dioxide bridged by the pyromellitic acid diimide into the polymer solution obtained in the step 1, wherein the nano-particles are between 20 and 90 percent o Dispersing for 0.5-24 hours under the condition of C, casting to form a film after uniform dispersion, and obtaining a polymer film after the solvent volatilizes, namely the lithium ion battery composite solid electrolyte film.
5. The method for preparing a composite solid polymer electrolyte according to claim 4, wherein the solvent in the step 1 and the step 2 comprises acetonitrile, acetone, N-Dimethylformamide (DMF), N-methylpyrrolidone (NMP), or water.
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