CN111224154A - Mesoporous nanoparticle gel composite electrolyte with lithium ion conduction and preparation method and application thereof - Google Patents
Mesoporous nanoparticle gel composite electrolyte with lithium ion conduction and preparation method and application thereof Download PDFInfo
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Abstract
The invention discloses a mesoporous nanoparticle gel composite electrolyte with lithium ion conduction and a preparation method and application thereof. The mesoporous lithium ion battery is prepared from surface-modified mesoporous nanoparticles, a polymer, an ionic liquid and a lithium salt; the surface-modified mesoporous nanoparticles are obtained by performing surface modification on mesoporous nanoparticles by using a silane coupling agent. The preparation method comprises the following steps: mixing a polymer, a lithium salt, surface modified mesoporous nano particles and an organic solvent, pouring the mixture onto a mold for casting to form a film, and drying the film in vacuum to obtain a composite electrolyte film; and then soaking in an ionic liquid solution of lithium salt to obtain the lithium ion battery. The electrolyte has high ionic conductivity and mechanical strength; the preparation method is simple, has the advantage of wide electrochemical window, and can be matched with the existing commercialized cathode material, so that the lithium ion battery with excellent performance can be prepared by using the gel composite electrolyte.
Description
Technical Field
The invention relates to a mesoporous nanoparticle gel composite electrolyte with lithium ion conduction and a preparation method and application thereof, belonging to the field of gel composite electrolytes.
Background
The lithium ion battery has the advantages of large capacity, high working voltage, small pollution, high safety performance and the like, and is a green and environment-friendly secondary energy battery. The gel composite electrolyte quasi-solid lithium ion battery has a very good application prospect, and is paid attention from various aspects, and the gel composite electrolyte also becomes one of hot spots in the research field of the lithium ion battery. The gel composite electrolyte has the advantages of high ionic conductivity, flexibility, good contact with an electrode interface and the like. Compared with a composite polymer electrolyte, the gel composite electrolyte has higher ionic conductivity and better thermal stability, and compared with an inorganic solid electrolyte, the gel composite electrolyte has the characteristics of simple preparation and flexibility. The currently widely researched PEO-based polymer electrolyte has the limitations of low ionic conductivity and low decomposition voltage, the ionic conductivity and mechanical property of the composite electrolyte prepared by adding inorganic filler can be improved, and the ionic conductivity of the composite electrolyte is 10-5～10-4Ionic conductivity 10 of conventional liquid lithium ion battery-3～10-2Compared with the prior art, the method has a large gap and cannot meet the requirement of large-scale application, so that the prepared flexible gel composite electrolyte has ionic conductivity comparable to that of a liquid lithium ion battery.
Disclosure of Invention
The invention aims to provide a mesoporous nanoparticle gel composite electrolyte with lithium ion conduction and a preparation method and application thereof, and the mesoporous nanoparticle gel composite electrolyte improves the mechanical property and the ionic conductivity of the electrolyte, so that the prepared gel composite electrolyte has the characteristics of high room-temperature conductivity, high mechanical strength and wide electrochemical window.
The invention provides a mesoporous nanoparticle gel composite electrolyte with lithium ion conduction, which is prepared from surface-modified mesoporous nanoparticles, a polymer, an ionic liquid and a lithium salt;
the surface-modified mesoporous nanoparticles are obtained by performing surface modification on mesoporous nanoparticles by using a silane coupling agent.
In the gel composite electrolyte, the mass ratio of the surface-modified mesoporous nanoparticles, the ionic liquid, the lithium salt and the polymer can be 0.5-6: 0.5-0.8: 2-6: 10.
In the gel composite electrolyte, the mesoporous nano particles are silicon-based mesoporous materials; specifically mesoporous silica, more specifically MCM41, SBA 15;
the silane coupling agent is selected from mercaptopropyltrimethoxysilane and/or mercaptopropyltriethoxysilane.
In the gel composite electrolyte, the method for preparing the surface modified mesoporous nanoparticles comprises the following steps: mixing the mesoporous nano particles with toluene, adding the silane coupling agent in an inert atmosphere, and carrying out heat preservation stirring reaction to obtain sulfhydrylated mesoporous silica; mixing and reacting the sulfhydrylated mesoporous silicon oxide with a hydrogen peroxide solution in the inert atmosphere to obtain a wet material; and adding the wet material into an aqueous solution of lithium nitrate, and stirring for reaction to obtain the surface modified mesoporous nano particles.
In the gel composite electrolyte, the mass ratio of the mesoporous nanoparticles to the silane coupling agent can be 1: 1.5-4, more specifically 1:2 or 1: 1.5-3;
the temperature of the heat preservation stirring reaction can be 30-50 ℃, more specifically 40 ℃ or 35-45 ℃, and the time can be 12-24 hours, more specifically 12 hours, 12-17 hours or 12-20 hours;
the mass percentage content of the hydrogen peroxide solution can be 10-30%, more specifically 30% or 20-30%; the reaction time with the hydrogen peroxide solution can be 6-10 h, more specifically 10h or 8-10 h;
the concentration of the aqueous solution of the lithium nitrate can be 1-2 mol/L, more specifically 1mol/L or 1-1.5 mol/L;
the reaction time after the lithium nitrate aqueous solution is added can be 6-10 hours, more specifically 6 hours or 6-8 hours;
the inert atmosphere comprises nitrogen or argon.
In the method for preparing the surface-modified mesoporous nanoparticles, the post-treatment of the heat-preservation stirring reaction is three times of ethanol and water washing and vacuum drying;
after the stirring reaction with the hydrogen peroxide solution is finished, washing with alcohol and water;
stirring and reacting with the lithium nitrate, washing with ethanol and water for three times, and drying in vacuum.
In the gel composite electrolyte, the polymer is at least one selected from polyvinylidene fluoride-hexafluoropropylene, polyethylene oxide and polyacrylonitrile;
the polymer polyvinylidene fluoride-hexafluoropropylene can have a weight average molecular weight of 30 x 104～50×104Specifically, it may be 40 × 104(ii) a The polyethylene oxide may have a weight average molecular weight of 60X 104～100×104Specifically, it may be 100 × 104(ii) a The polyacrylonitrile may have a weight average molecular weight of 15 × 104～30×104。
In the gel composite electrolyte, the ionic liquid is at least one of 1-ethyl-3-methylimidazoline bis (trifluoromethylsulfonyl) imide, 1-hexyl-3-methylpyridine bis (trifluoromethylsulfonyl) imide salt and 1- (2-hydroxyethyl) -3-methylimidazoline bis (trifluoromethylsulfonyl) imide salt.
In the gel composite electrolyte, the lithium salt is bis (trifluoromethanesulfonimide) lithium and/or lithium perchlorate.
The mesoporous nano particle gel composite electrolyte with lithium ion conduction has the advantages of lithium ion conduction function, improved mechanical property and high room temperature conductivity.
The mesoporous nanoparticle gel composite electrolyte with lithium ion conduction in the embodiment of the invention has the ionic conductivity of 1.301 multiplied by 10 at 20 DEG C-3S/cm。
The invention also provides a preparation method of the mesoporous nanoparticle gel composite electrolyte with lithium ion conduction, which comprises the following steps: 1) mixing the polymer, the lithium salt, the surface modified mesoporous nano particles and an organic solvent, pouring the mixture onto a mold for casting to form a film, and drying the film in vacuum to obtain a composite electrolyte film;
2) and soaking the composite electrolyte membrane in the ionic liquid solution of the lithium salt to obtain the mesoporous nanoparticle gel composite electrolyte with lithium ion conduction.
In the above preparation method, the organic solvent is acetonitrile and/or acetone;
the material of the mould is polytetrafluoroethylene;
in the step 2), the soaking time can be 4-8 h; specifically, the time period can be 6 hours, 4 hours to 6 hours, 6 hours to 8 hours, 5 hours to 7 hours or 4.5 hours to 7.5 hours.
In the preparation method, in the step 1), the mass ratio of the polymer, the lithium salt and the surface-modified mesoporous nanoparticles can be 10: 3-4: 0.5-6, and specifically can be 1:0.3263:0.1, 1:0.3263:0.2, 1:0.3263:0.3, 1:0.3263:0.4 or 10: 3-4: 1-4;
in the step 2), the molar concentration of the ionic liquid solution of the lithium salt may be 0.6 to 2mol/L, and specifically may be 1mol/L or 0.6 to 1 mol/L.
The invention relates to an application of a mesoporous nanoparticle gel composite electrolyte with lithium ion conduction in the preparation of a lithium ion battery.
The invention also provides a lithium ion battery, and the electrolyte of the lithium ion battery is the mesoporous nanoparticle gel composite electrolyte with lithium ion conduction.
The invention further provides surface-modified mesoporous nanoparticles, which are the surface-modified mesoporous nanoparticles in the gel composite electrolyte.
The preparation method of the surface modified mesoporous nanoparticles comprises the following steps: mixing the mesoporous nano particles with toluene, adding the silane coupling agent in an inert atmosphere, and carrying out heat preservation stirring reaction to obtain sulfhydrylated mesoporous silica; mixing and reacting the sulfhydrylated mesoporous silicon oxide with a hydrogen peroxide solution in the inert atmosphere to obtain a wet material; and adding the wet material into an aqueous solution of lithium nitrate, and stirring for reaction to obtain the surface modified mesoporous nano particles.
In the preparation method of the surface-modified mesoporous nanoparticles, the mass ratio of the mesoporous nanoparticles to the silane coupling agent can be 1: 1.5-4, more specifically 1:2 or 1: 1.5-3;
the temperature of the heat preservation stirring reaction can be 30-50 ℃, more specifically 40 ℃ or 35-45 ℃, and the time can be 12-24 hours, more specifically 12 hours, 12-17 hours or 12-20 hours;
the mass percentage content of the hydrogen peroxide solution can be 10-30%, more specifically 30% or 20-30%; the reaction time with the hydrogen peroxide solution can be 6-10 h, more specifically 10h or 8-10 h;
the concentration of the aqueous solution of the lithium nitrate can be 1-2 mol/L, more specifically 1mol/L or 1-1.5 mol/L;
the reaction time after the lithium nitrate aqueous solution is added can be 6-10 hours, more specifically 6 hours or 6-8 hours;
the inert atmosphere comprises nitrogen or argon.
In the method for preparing the surface-modified mesoporous nanoparticles, the post-treatment of the heat-preservation stirring reaction is three times of ethanol and water washing and vacuum drying;
after the stirring reaction with the hydrogen peroxide solution is finished, washing with alcohol and water;
stirring and reacting with the lithium nitrate, washing with ethanol and water for three times, and drying in vacuum.
The method for preparing the surface-modified mesoporous nanoparticles specifically comprises the following steps: toluene and mesoporous nano particles are added into a three-mouth bottle, and N is2Stirring for 60min in the atmosphere, slowly dropwise adding a silane coupling agent, keeping the temperature and stirring for 12h at 40 ℃, washing with ethanol and water for three times, and vacuum-drying for 12h at 40 ℃ to obtain sulfhydrylated mesoporous silica; putting the product in 30% hydrogen peroxide solution N2Stirring for 10 hours in the atmosphere, and washing the product with alcohol to obtain a wet material; and adding the wet material into 1mol/L lithium nitrate, stirring for 6 hours, washing with ethanol and water for three times, and performing vacuum drying to obtain the surface-modified mesoporous silica, which is marked as MCM 41-Li.
The invention has the following advantages:
the inventionThe ionic conductivity and the mechanical strength of the electrolyte prepared by adding the surface-modified mesoporous nanoparticles are greatly improved compared with the electrolyte prepared by adding the unmodified mesoporous nanoparticles, and the ionic conductivity and the mechanical strength of the electrolyte can be respectively improved by 5-8 times and 2-3 times. The preparation method is simple, the electrolyte membrane prepared by adding the surface modified mesoporous nano particles is soaked in the ionic liquid solution to prepare the gel composite electrolyte, and the mechanical strength of the obtained electrolyte membrane is equivalent to that of the electrolyte prepared by directly adding the mesoporous nano particles. The mesoporous adsorption ionic liquid improves the ionic conductivity, and the ionic conductivity is 1.301mS cm at 20 DEG C-1The electrolyte membrane soaked in the ionic liquid has the advantage of wide electrochemical window, particularly the electrochemical window of about 4.8V, and can be matched with the conventional commercialized cathode material, so that the lithium ion battery with excellent performance can be prepared by using the gel composite electrolyte.
Drawings
FIG. 1 is a specific synthetic route of mesoporous nanoparticles with Li ion conduction/strong electronegativity characteristics according to the present invention.
FIG. 2 is an Arrhenius plot of comparative example 1 sample PEO/LiTFSI/PVDF-HFP/0.2g MCM41, comparative example 2 sample PEO/LiTFSI/PVDF-HFP/0.2g SBA15, inventive example 1 sample PEO/LiTFSI/PVDF-HFP/0.2g surface-modified mesoporous nanoparticles (MCM41-Li), inventive example 2 sample PEO/LiTFSI/PVDF-HFP/0.2g surface-modified mesoporous nanoparticles (SBA 15-Li).
FIG. 3 is a stress-strain test chart of comparative example 1 sample PEO/LiTFSI/PVDF-HFP/0.2g MCM41, comparative example 2 sample PEO/LiTFSI/PVDF-HFP/0.2g SBA15, inventive example 1 sample PEO/LiTFSI/PVDF-HFP/0.2g surface-modified mesoporous nanoparticles (MCM41-Li), inventive example 2 sample PEO/LiTFSI/PVDF-HFP/0.2g surface-modified mesoporous nanoparticles (SBA15-Li), with strain on the abscissa and stress on the ordinate.
Fig. 4 is a stress-strain test chart of the composite electrolyte prepared by adding the surface-modified mesoporous nanoparticles (MCM41-Li) of different masses (0.1, 0.2, 0.3, 0.4g) prepared in example 1 of the present invention, with strain on the abscissa and stress on the ordinate.
FIG. 5 is a stress-strain test chart of the composite electrolyte prepared by adding mesoporous nanoparticles (MCM41) of different masses (0, 0.1, 0.2, 0.3g) according to comparative example 1 of the present invention, with strain on the abscissa and stress on the ordinate.
FIG. 6 is an Arrhenius plot of composite electrolytes prepared by adding surface-modified mesoporous nanoparticles (MCM41-Li) of different masses (0.1, 0.2, 0.3g) according to example 1 of the present invention.
FIG. 7 is an Arrhenius plot of composite electrolytes prepared by adding mesoporous nanoparticles (MCM41) of different masses (0, 0.1, 0.2, 0.3g) according to comparative example 1 of the present invention.
FIG. 8 is an impedance spectrum of a gel composite electrolyte prepared by adding 0.3g of surface-modified mesoporous nanoparticles (MCM41-Li) prepared in example 3 of the present invention.
FIG. 9 is a linear sweep voltammetry test chart of a gel composite electrolyte prepared by adding 0.3g of surface-modified mesoporous nanoparticles (MCM41-Li) prepared in example 3 of the present invention.
Detailed Description
The experimental procedures used in the following examples are all conventional procedures unless otherwise specified.
Materials, reagents and the like used in the following examples are commercially available unless otherwise specified.
The present invention will be described in detail below with reference to specific examples.
Example 1 PEO/LiTFSI/PVDF-HFP/surface modified mesoporous nanoparticles (MCM41-Li)
Synthesizing the surface modified mesoporous nano particles: the synthetic route is shown in figure 1, and the specific steps are as follows: a100 mL three-necked flask was charged with 50mL toluene and 1.5g mesoporous silica MCM41, N2Stirring for 60min in the atmosphere, slowly dropwise adding 3g of MPTMS (mercaptopropyltrimethoxysilane), keeping the temperature and stirring for 12h at 40 ℃, washing with ethanol and water for three times, and vacuum-drying for 12h at 40 ℃ to obtain sulfhydrylated mesoporous silica; putting the product in 30% hydrogen peroxide solution N2Stirring for 10 hours in the atmosphere, and washing the product with alcohol to obtain a wet material; adding the wet material into 1mol/L lithium nitrate, stirring for 6h, washing with ethanol and water for three times, and vacuum drying to obtain the surface-modified mesoporous nano-particlesParticles, designated MCM 41-Li.
Preparation of a composite electrolyte membrane: dissolving 0.5g of polyvinylidene fluoride-hexafluoropropylene (weight average molecular weight Mw is 400000) into 5mL of acetone, dissolving 0.3263g of lithium bis (trifluoromethanesulfonylimide), 0.1-0.4 g of surface modified mesoporous nanoparticles (MCM41-Li) and 0.5g of polyethylene oxide (Mw is 1000000) into 10mL of acetonitrile, mixing and uniformly stirring the two dissolved solutions, pouring the mixture onto a clean polytetrafluoroethylene mold for casting to form a film, and performing vacuum drying at the relative vacuum degree value of-0.1 to-0.08 MPa and the temperature of 60 ℃ to obtain a composite electrolyte film, namely PEO/LiTFSI/PVDF-HFP/surface modified mesoporous nanoparticles (MCM 41-Li).
As can be seen from the data in fig. 4 and 5, the mechanical strength of the electrolyte membrane prepared by surface-modifying mesoporous nanoparticles in the composite electrolyte membrane prepared in this example can reach 5.27MPa, which is 2.38 times higher than the mechanical strength (2.21MPa) of the electrolyte membrane prepared in comparative example 1, and the wettability between the surface of the modified inorganic filler and the polymer is increased, and the rigid contact between the polymer and the inorganic substance is changed into the flexible contact between the polymer and the surface-modified groups of the inorganic substance, so that the mechanical strength is improved. As can be seen from the data in FIGS. 6 and 7, the ionic conductivity of the composite electrolyte prepared by adding mesoporous nanoparticles and surface-modified mesoporous nanoparticles at 20 ℃ is 6.14X 10-6The S/cm is increased to 3.29 multiplied by 10-5S/cm, the mesoporous nano particle surface is modified to have lithium ion transmission capacity so as to improve the ion conductivity.
Example 2 PEO/LiTFSI/PVDF-HFP/surface modified mesoporous nanoparticles (SBA15-Li)
Synthesizing the surface modified mesoporous nano particles: the method is the same as the method in the embodiment 1 of the invention, but the difference is that the mesoporous silicon oxide is SBA15, and the surface modified mesoporous nano particle is obtained and is marked as SBA 15-Li.
Preparation of a composite electrolyte membrane: dissolving 0.5g of polyvinylidene fluoride-hexafluoropropylene (Mw is 400000) into 5ml of acetone, dissolving 0.3263g of lithium bis (trifluoromethanesulfonyl) imide, 0.1-0.4 g of surface modified mesoporous nanoparticles (SBA15-Li) and 0.5g of polyethylene oxide (Mw is 1000000) into 10ml of acetonitrile, mixing and uniformly stirring the two dissolved solutions, pouring the mixture onto a dry and static polytetrafluoroethylene mold for casting to form a film, and performing vacuum drying to obtain a composite electrolyte film, wherein the composite electrolyte film is also called PEO/LiTFSI/PVDF-HFP/surface modified mesoporous nanoparticles (SBA 15-Li).
As can be seen from the arrhenius curve of fig. 2, the composite electrolyte membrane prepared in the present embodiment has improved ionic conductivity due to the lithium ion transport ability of the surface-modified mesoporous nanoparticles, compared to the comparative example. As can be seen from fig. 3, in the composite electrolyte membrane prepared in this embodiment, compared with the comparative example, the mechanical strength of the electrolyte membrane prepared by adding 0.2g of mesoporous nanoparticles MCM41 and SBA15 is 2.21MPa and 2.18MPa, the mechanical strength of the electrolyte membrane prepared by adding the same mass of surface-modified mesoporous nanoparticles MCM41-Li and SBA15-Li is 3.72 MPa and 3.21MPa, the wettability between the surface-modified mesoporous nanoparticles and the polymer is increased, and the rigid contact between the polymer and the inorganic substance is changed into the flexible contact between the polymer and the surface modification groups of the inorganic substance, so that the mechanical strength is improved.
Example 3 PEO/LiTFSI/PVDF-HFP/surface modified mesoporous nanoparticle (MCM41-Li) gel composite electrolyte
The composite electrolyte membrane prepared in the embodiment 1 of the present invention is soaked in 1mol/L solution of 1-ethyl-3-methylimidazoline bis (trifluoromethylsulfonyl) imide ([ EMIm ] TFSI) of bis (trifluoromethylsulfonyl) imide lithium for 6 hours to obtain a target gel composite electrolyte membrane (i.e., mesoporous nanoparticle gel composite electrolyte with lithium ion conduction), which is also called PEO/LiTFSI/PVDF-HFP/surface modified mesoporous nanoparticle (MCM41-Li) gel composite electrolyte.
As can be seen from fig. 8, the gel composite electrolyte prepared in this example has an ionic conductivity of 3.29 × 10 at 20 ℃ in the composite electrolyte of example 1 of the present invention, compared to the composite electrolyte prepared in example 1-5S/cm, the ionic conductivity of the electrolyte of this example at 20 ℃ is 1.301X 10-3S/cm. The surface-modified mesoporous nanoparticles still have a complete mesoporous structure, and after the mesoporous nanoparticles are soaked in the ionic liquid, the mesoporous particles absorb the ionic liquid, so that the mesopores become a fast transmission channel of lithium ions, and the ionic conductivity is greatly improved. As can be seen from FIG. 9, the soaking stepThe electrolyte membrane after the ionic liquid has an electrochemical window of about 4.8V and can be matched with the existing commercialized cathode material.
Comparative examples 1,
Preparation of PEO/LiTFSI/PVDF-HFP/mesoporous nanoparticles (MCM 41):
dissolving 0.5g of polyvinylidene fluoride-hexafluoropropylene (Mw is 400000) into 5ml of acetone, dissolving 0.3263g of lithium bis (trifluoromethanesulfonimide), 0-0.3 g of mesoporous silica (MCM41) and 0.5g of polyethylene oxide (Mw is 1000000) into 10ml of acetonitrile, mixing and uniformly stirring the two dissolved solutions, pouring the mixture onto a dry and static polytetrafluoroethylene mold for casting to form a film, and performing vacuum drying to obtain a composite electrolyte film, namely PEO/LiTFSI/PVDF-HFP/mesoporous nanoparticles (MCM 41).
Comparative examples 2,
Preparation of PEO/LiTFSI/PVDF-HFP/mesoporous nanoparticles (SBA 15):
dissolving 0.5g of polyvinylidene fluoride-hexafluoropropylene (Mw of 400000) into 5ml of acetone, dissolving 0.3263g of lithium bis (trifluoromethanesulfonimide), 0-0.3 g of mesoporous silica (SBA15) and 0.5g of polyethylene oxide (Mw of 1000000) into 10ml of acetonitrile, mixing and uniformly stirring the two dissolved solutions, pouring the mixture onto a dry and static polytetrafluoroethylene mold for casting to form a film, and performing vacuum drying to obtain a composite electrolyte film, namely PEO/LiTFSI/PVDF-HFP/mesoporous nanoparticles (SBA 15).
Claims (10)
1. A mesoporous nanoparticle gel composite electrolyte with lithium ion conduction is prepared from surface-modified mesoporous nanoparticles, a polymer, an ionic liquid and a lithium salt;
the surface-modified mesoporous nanoparticles are obtained by performing surface modification on mesoporous nanoparticles by using a silane coupling agent.
2. The gel composite electrolyte of claim 1, wherein: the mass ratio of the surface-modified mesoporous nanoparticles, the ionic liquid, the lithium salt and the polymer is 0.5-6: 0.5-0.8: 2-6: 10;
the mesoporous nano particles are silicon-based mesoporous materials;
the silane coupling agent is selected from mercaptopropyltrimethoxysilane and/or mercaptopropyltriethoxysilane.
3. The gel composite electrolyte according to claim 1 or 2, characterized in that: the method for preparing the surface-modified mesoporous nanoparticles comprises the following steps: mixing the mesoporous nano particles with toluene, adding the silane coupling agent in an inert atmosphere, and carrying out heat preservation stirring reaction to obtain sulfhydrylated mesoporous silica; mixing and reacting the sulfhydrylated mesoporous silicon oxide with a hydrogen peroxide solution in the inert atmosphere to obtain a wet material; and adding the wet material into an aqueous solution of lithium nitrate, and stirring for reaction to obtain the surface modified mesoporous nano particles.
4. The gel composite electrolyte of claim 3, wherein: the mass ratio of the mesoporous nanoparticles to the silane coupling agent is 1: 1.5-4;
the temperature of the heat preservation stirring reaction is 30-50 ℃, and the time is 12-24 hours;
the mass percentage content of the hydrogen peroxide solution is 10-30%; the reaction time with the hydrogen peroxide solution is 6-10 h;
the concentration of the aqueous solution of the lithium nitrate is 1-2 mol/L;
the reaction time after the lithium nitrate aqueous solution is added is 6-10 h;
the inert atmosphere comprises nitrogen or argon.
5. The gel composite electrolyte according to any one of claims 1 to 4, characterized in that: the polymer is selected from at least one of polyvinylidene fluoride-hexafluoropropylene, polyethylene oxide and polyacrylonitrile;
the weight average molecular weight of the polymer polyvinylidene fluoride-hexafluoropropylene is 30 multiplied by 104～50×104(ii) a The polyethylene oxide has a weight average molecular weight of 60X 104～100×104(ii) a The weight average molecular weight of the polyacrylonitrile is 15 multiplied by 104～30×104；
The ionic liquid is at least one of 1-ethyl-3-methylimidazoline bis (trifluoromethylsulfonyl) imide, 1-hexyl-3-methylpyridine bis (trifluoromethylsulfonyl) imide salt and 1- (2-hydroxyethyl) -3-methylimidazoline bis (trifluoromethylsulfonyl) imide salt;
the lithium salt is bis (trifluoromethanesulfonyl) imide lithium and/or lithium perchlorate.
6. The method for preparing the mesoporous nanoparticle gel composite electrolyte according to any one of claims 1 to 5, comprising the steps of: 1) mixing the polymer, the lithium salt, the surface modified mesoporous nano particles and an organic solvent, pouring the mixture onto a mold for casting to form a film, and drying the film in vacuum to obtain a composite electrolyte film;
2) and soaking the composite electrolyte membrane in the ionic liquid solution of the lithium salt to obtain the mesoporous nanoparticle gel composite electrolyte with lithium ion conduction.
7. The method of claim 6, wherein: the organic solvent is acetonitrile and/or acetone;
the material of the mould is polytetrafluoroethylene;
in the step 2), the soaking time is 4-8 h;
in the step 1), the mass ratio of the polymer, the lithium salt and the surface modified mesoporous nanoparticles is 10: 3-4: 0.5-6;
in the step 2), the molar concentration of the ionic liquid solution of the lithium salt is 0.6-2 mol/L.
8. Use of the mesoporous nanoparticle gel composite electrolyte with lithium ion conductivity according to any one of claims 1 to 5 for the preparation of a lithium ion battery.
9. The surface-modified mesoporous nanoparticles in the gel composite electrolyte according to any one of claims 1 to 5.
10. The preparation method of the surface-modified mesoporous nanoparticles of claim 9, comprising the following steps: mixing the mesoporous nano particles with toluene, adding the silane coupling agent in an inert atmosphere, and carrying out heat preservation stirring reaction to obtain sulfhydrylated mesoporous silica; mixing and reacting the sulfhydrylated mesoporous silicon oxide with a hydrogen peroxide solution in the inert atmosphere to obtain a wet material; adding the wet material into an aqueous solution of lithium nitrate, and stirring for reaction to obtain the surface modified mesoporous nanoparticles;
the mass ratio of the mesoporous nanoparticles to the silane coupling agent is 1: 1.5-4;
the temperature of the heat preservation stirring reaction is 30-50 ℃, and the time is 12-24 hours;
the mass percentage content of the hydrogen peroxide solution is specifically 10-30%; the reaction time with the hydrogen peroxide solution is specifically 6-10 h;
the concentration of the aqueous solution of the lithium nitrate is 1-2 mol/L;
the reaction time after the lithium nitrate aqueous solution is added is specifically 6-10 h;
the inert atmosphere comprises nitrogen or argon.
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| CN112864457A (en) * | 2021-01-29 | 2021-05-28 | 惠州锂威新能源科技有限公司 | Preparation method of composite solid electrolyte and product thereof |
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| CN116960575A (en) * | 2023-08-08 | 2023-10-27 | 沧州中孚新能源材料有限公司 | High-strength gel electrolyte diaphragm and preparation method and application thereof |
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