CN112909316A - Commercial diaphragm-based sandwich-structure polymer composite solid electrolyte membrane and preparation method thereof - Google Patents

Commercial diaphragm-based sandwich-structure polymer composite solid electrolyte membrane and preparation method thereof Download PDF

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CN112909316A
CN112909316A CN202110063274.5A CN202110063274A CN112909316A CN 112909316 A CN112909316 A CN 112909316A CN 202110063274 A CN202110063274 A CN 202110063274A CN 112909316 A CN112909316 A CN 112909316A
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solid electrolyte
electrolyte membrane
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composite solid
diaphragm
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石琨
许争杰
张卫新
杨则恒
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Hefei University of 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
    • H01M10/052—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
    • 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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Abstract

The invention discloses a polymer composite solid electrolyte membrane with a commercial diaphragm-based sandwich structure and a preparation method thereof. Compared with a single polymer solid electrolyte membrane, the polymer composite solid electrolyte membrane with the sandwich structure provided by the invention has the advantages that the mechanical property, the electrochemical stability and the cycling stability to lithium are obviously improved, and the technical scheme provided by the invention is simple in process, easy to implement and beneficial to popularization and application.

Description

Commercial diaphragm-based sandwich-structure polymer composite solid electrolyte membrane and preparation method thereof
Technical Field
The invention belongs to the field of preparation of lithium ion polymer solid electrolyte membranes, and particularly relates to a commercial diaphragm-based sandwich-structured polymer composite solid electrolyte membrane and a preparation method thereof.
Background
The lithium ion battery has the advantages of high energy density, long cycle life, no memory effect and the like, and is widely applied to the fields of portable electronic equipment, power grid energy storage systems, new energy automobiles and the like as a new generation of energy storage equipment. As the demand for lithium ion batteries increases, the safety performance of the batteries is receiving more and more attention. However, the liquid organic electrolyte used in the conventional lithium ion battery may cause a series of safety problems such as leakage, flammability and even explosion, which limits further development and application. Compared with the traditional liquid electrolyte, the solid electrolyte has the advantages of low flammability, high thermal stability, no leakage and low explosion risk, and can obviously improve the safety performance of the lithium ion battery.
The electrolyte of the solid lithium ion battery is mainly divided into an inorganic solid electrolyte and a polymer solid electrolyte. The inorganic solid electrolyte has higher lithium ion conductivity and wider electrochemical window, but has complex preparation process, high energy consumption and large interfacial resistance with electrodes. Although the polymer solid electrolyte has simple preparation process, easy film formation, bending resistance and excellent compatibility with an interface between electrodes, the polymer solid electrolyte has the defects of low lithium ion conductivity at room temperature, poor mechanical property and the like.
In order to solve the above problems of the single inorganic solid electrolyte or the polymer solid electrolyte, researchers have prepared various types of polymer composite solid electrolytes by designing a cross-linked structure, adding a plasticizer or blending a ceramic filler, etc., based on the polymer solid electrolyte. The polymer composite solid electrolyte integrates the performance advantages of a single inorganic solid electrolyte and a polymer solid electrolyte, such as obviously improved lithium ion conductivity, mechanical property, excellent interface compatibility and the like. However, the composite polymer solid electrolyte prepared by the methods still has better room-temperature electrochemical cycling stability and lithium stability, and the preparation process is more complex, has higher energy consumption, and is not beneficial to large-scale production and application.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide a universal and feasible polymer composite solid electrolyte, wherein a polymer composite membrane with a sandwich structure is constructed by introducing a commercial diaphragm so as to remarkably improve the mechanical property, the room-temperature electrochemical stability and the cycling stability of the polymer solid electrolyte. The invention also provides a preparation method of the commercial membrane-based sandwich structure polymer composite solid electrolyte membrane.
In order to achieve the purpose, the invention adopts the following technical scheme:
the polymer composite solid electrolyte membrane with the commercial diaphragm-based sandwich structure is of a sandwich structure, wherein polymer layers are arranged on two sides of a commercial diaphragm; the polymer layer is formed by coating a polymer slurry and drying. In the preparation process of the polymer composite solid electrolyte, the polymer slurry can be immersed into the porous commercial diaphragm to form an integrated sandwich structure. Lithium ions are transmitted in the polymer composite solid electrolyte membrane with the sandwich structure through chain segment motion of the polymer. The polymer composite solid electrolyte membrane with the sandwich structure provided by the invention has excellent mechanical properties, can effectively inhibit the growth of lithium dendrites, and shows excellent room-temperature electrochemical cycling stability and lithium stability.
In the technical scheme of the polymer composite solid electrolyte membrane with the sandwich structure, the commercial diaphragm is at least one of a Polyethylene (PE) diaphragm, a polypropylene (PP) diaphragm, a ceramic coating PE diaphragm, a ceramic coating PP diaphragm, a double-layer PP/PE diaphragm and a three-layer PP/PE/PP diaphragm.
In the technical scheme of the polymer composite solid electrolyte membrane with the sandwich structure, the components of the polymer slurry comprise a polymer matrix, lithium salt and inorganic filler. The polymer matrix is at least one of polyethylene oxide (PEO), polyvinylidene fluoride (PVDF), polyvinylidene fluoride-co-hexafluoropropylene (PVDF-HFP), polymethyl methacrylate (PMMA), Polyacrylonitrile (PAN), polyethylene glycol (PEG), polyvinyl alcohol (PVA), polyvinyl chloride (PVC) and polypropylene carbonate (PPC). The lithium salt is lithium perchlorate (LiClO)4) Lithium bistrifluoromethylsulfonyl imide (LiTFSI), lithium bistrifluorosulfonimide (LiFSI), lithium nitrate (LiNO)3) Lithium borate (LiBO)3) And lithium chloride (LiCl)And (4) seed preparation. The inorganic filler is SiO2、Al2O3、TiO2、ZnO、Li0.3La0.557TiO3(LLTO)、Li1.3Al0.3Ti1.7(PO4)3(LATP)、Li7La3Zr2O12(LLZO)、Li6PS5Cl and Li6.4La3Zr1.4Ta0.6O12(LLZTO).
In the above technical solution of the sandwich-structured polymer composite solid electrolyte membrane, the polymer matrices on both sides of the commercialized separator may be the same or different.
In the technical scheme of the polymer composite solid electrolyte membrane with the sandwich structure, from the viewpoint of battery performance, the thickness of the composite solid electrolyte membrane is preferably 30-200 mu m, the thickness of a commercial diaphragm layer is 20-40 mu m, the thickness of a single-side polymer electrolyte layer is 5-100 mu m, and the thickness ratio of two-side polymer electrolyte layers is 1:1-1: 9.
The invention also provides a preparation method of the commercial diaphragm-based sandwich-structure polymer composite solid electrolyte membrane, which comprises the following steps:
step 1, uniformly dissolving or dispersing a polymer matrix, lithium salt and an inorganic filler in a polar solvent under a water bath condition of 40-65 ℃ to obtain polymer slurry; in the polymer slurry, the mass fraction of a polymer matrix is 5-20%, the mass fraction of lithium salt is 3-20%, and the mass fraction of an inorganic filler is 0-10%.
Step 2, uniformly coating the polymer slurry on one side of a commercial diaphragm, and drying to form a film; and then uniformly coating the polymer slurry on the other side of the commercial diaphragm, and drying to form a film, thus obtaining the target product, namely the commercial diaphragm-based sandwich-structured polymer composite solid electrolyte film.
In the preparation method of the commercial diaphragm-based sandwich-structure polymer composite solid electrolyte membrane, the polar solvent in the step 1 is at least one of N, N-Dimethylformamide (DMF), N-methylpyrrolidone (NMP) and anhydrous Acetonitrile (ACN).
In the preparation method of the commercial diaphragm-based sandwich-structure polymer composite solid electrolyte membrane, in the step 2, the first drying is carried out for 2-7 hours in a vacuum oven at 40-100 ℃, and the second drying is carried out for 17-22 hours in the vacuum oven at 40-100 ℃.
Compared with the prior art, the technical scheme of the invention has the following beneficial effects:
the invention provides a general method for constructing a polymer composite solid electrolyte with a sandwich structure based on a commercial lithium ion battery diaphragm, which can realize the preparation of diversified polymer composite solid electrolytes with the sandwich structure by uniformly coating lithium ion conduction polymer matrixes with different components or types on two sides of the diaphragm. The polymer composite solid electrolyte membrane with the sandwich structure provided by the invention has excellent mechanical properties, can effectively inhibit the growth of lithium dendrites, and shows excellent room-temperature electrochemical cycling stability and lithium stability. The preparation method is universal, feasible, economical and effective, and is beneficial to realizing the large-scale production of the polymer composite solid electrolyte with the sandwich structure.
Drawings
Fig. 1 is a cross-sectional scanning electron micrograph of a polymer composite solid electrolyte membrane of a sandwich structure prepared in example 1.
Fig. 2 is a graph showing the room temperature cycle characteristics of the sandwich structure polymer composite solid electrolyte membrane prepared in example 1 and the PVDF polymer solid electrolyte membrane prepared in comparative example 1.
FIG. 3 is a graph showing the room temperature cycle performance of the polymer composite solid electrolyte membrane having a sandwich structure prepared in example 2 and the PVDF/LLZTO polymer solid electrolyte membrane prepared in comparative example 2.
Fig. 4 is a graph showing room temperature vs. lithium stability tests of the sandwich structure polymer composite solid electrolyte membrane prepared in example 1 and the PVDF polymer solid electrolyte membrane prepared in comparative example 1.
Fig. 5 is a graph showing mechanical properties of the sandwich-structured polymer composite solid electrolyte membrane prepared in example 1 and the PVDF polymer solid electrolyte membrane prepared in comparative example 1.
Detailed Description
The present invention provides a polymer composite solid electrolyte membrane with a sandwich structure and a method for preparing the same, which are further described below with reference to examples. It should be noted that the following examples are only for illustrating the present invention and should not be construed as limiting the scope of the present invention, and those skilled in the art can make certain insubstantial modifications and adaptations of the present invention based on the above disclosure and still fall within the scope of the present invention.
Example 1
In this example, a commercial polymer composite solid electrolyte membrane with a membrane-based sandwich structure was prepared as follows:
step 1, under the condition of water bath at 45 ℃, PVDF and LiClO are mixed4Dissolving in DMF to obtain uniform PVDF/LiClO4Polymer paste, wherein the mass fraction of PVDF is 10%, LiClO4Is 3.33 percent.
Step 2, uniformly coating the polymer slurry prepared in the step 1 on one side of a PP diaphragm, and drying at 60 ℃ for 5 hours to form a film; and (3) uniformly coating the polymer slurry prepared in the step (1) on the other side of the PP diaphragm, and drying at 60 ℃ for 19h to form a film, thus obtaining the commercial diaphragm-based sandwich-structured polymer composite solid electrolyte film of the target product.
Comparative example 1
In this comparative example, a single polymer composite solid electrolyte membrane was prepared by the following steps:
step 1, under the condition of water bath at 45 ℃, PVDF and LiClO are mixed4Dissolving in DMF to obtain uniform PVDF/LiClO4Polymer paste, wherein the mass fraction of PVDF is 10%, LiClO4Is 3.33 percent.
And 2, uniformly coating the polymer slurry obtained in the step 1 on a glass plate, and drying for 24 hours at the temperature of 60 ℃ to form a film, thereby obtaining the PVDF polymer solid electrolyte film.
Example 2
In this example, a commercial polymer composite solid electrolyte membrane with a membrane-based sandwich structure was prepared as follows:
step 1, dissolving PVDF, LiTFSI and LLZTO in DMF under the condition of water bath at 45 ℃ to obtain uniform polymer slurry, wherein the mass fraction of PVDF is 10%, the mass fraction of LiTFSI is 3.33% and the mass fraction of LLZTO is 1%.
Step 2, uniformly coating the polymer slurry prepared in the step 1 on one side of a PP diaphragm, and drying at 60 ℃ for 5 hours to form a film; and (3) uniformly coating the polymer slurry prepared in the step (1) on the other side of the PP diaphragm, and drying at 60 ℃ for 19h to form a film, thus obtaining the commercial diaphragm-based sandwich-structured polymer composite solid electrolyte film of the target product.
Comparative example 2
In this comparative example, a single polymer composite solid electrolyte membrane was prepared by the following steps:
step 1, dissolving PVDF, LiTFSI and LLZTO in DMF under the condition of water bath at 45 ℃ to obtain uniform polymer slurry, wherein the mass fraction of PVDF is 10%, the mass fraction of LiTFSI is 3.33% and the mass fraction of LLZTO is 1%.
And 2, uniformly coating the polymer slurry obtained in the step 1 on a glass plate, and drying at 60 ℃ for 24 hours to form a film, thereby obtaining the PVDF/LLZTO polymer solid electrolyte film.
Example 3
In this example, a commercial polymer composite solid electrolyte membrane with a membrane-based sandwich structure was prepared as follows:
step 1, under the condition of water bath at 45 ℃, PEO, LiTFSI and SiO2Dissolving in ACN to obtain uniform polymer slurry, wherein the mass fraction of PEO is 9%, the mass fraction of LiTFSI is 6%, and SiO is2Is 2 percent.
Step 2, uniformly coating the polymer slurry prepared in the step 1 on one side of the PE diaphragm, and drying at 60 ℃ for 5 hours to form a film; and (3) uniformly coating the polymer slurry prepared in the step (1) on the other side of the PE diaphragm, and drying at 60 ℃ for 19h to form a film, thus obtaining the commercial diaphragm-based sandwich-structured polymer composite solid electrolyte film of the target product.
Comparative example 3
In this comparative example, a single polymer composite solid electrolyte membrane was prepared by the following steps:
step 1, under the condition of water bath at 45 ℃, PEO, LiTFSI and SiO2Dissolved in ACN, a uniform polymer slurry was obtained in which the mass fraction of PEO was 9%, the mass fraction of LiTFSI was 6%, and SiO2Is 2 percent.
Step 2, uniformly coating the polymer slurry obtained in the step 1 on a glass plate, and drying for 24 hours at the temperature of 60 ℃ to form a film to obtain PEO/SiO2A polymer solid electrolyte membrane.
Example 4
In this example, a commercial polymer composite solid electrolyte membrane with a membrane-based sandwich structure was prepared as follows:
step 1, dissolving PAN, LiCl and LLTO in DMF under the condition of water bath at 45 ℃ to obtain uniform polymer slurry, wherein the mass fraction of PAN is 10%, the mass fraction of LiCl is 10% and the mass fraction of LLTO is 5%.
Step 2, uniformly coating the polymer slurry prepared in the step 1 on one side of the PE diaphragm, and drying at 60 ℃ for 5 hours to form a film; and (3) uniformly coating the polymer slurry prepared in the step (1) on the other side of the PE diaphragm, and drying at 60 ℃ for 19h to form a film, thus obtaining the commercial diaphragm-based sandwich-structured polymer composite solid electrolyte film of the target product.
Comparative example 4
In this comparative example, a single polymer composite solid electrolyte membrane was prepared by the following steps:
step 1, dissolving PAN, LiCl and LLTO in DMF under the condition of water bath at 45 ℃ to obtain uniform polymer slurry, wherein the mass fraction of PAN is 10%, the mass fraction of LiCl is 10% and the mass fraction of LLTO is 5%.
And 2, uniformly coating the polymer slurry obtained in the step 1 on a glass plate, and drying at 60 ℃ for 24 hours to form a film, thereby obtaining the PAN/LLTO polymer solid electrolyte film.
Example 5
In this example, a commercial polymer composite solid electrolyte membrane with a membrane-based sandwich structure was prepared as follows:
step 1, dissolving PPC, LiTFSI and LATP in NMP under the condition of water bath at 45 ℃ to obtain uniform polymer slurry, wherein the mass fraction of PPC is 5%, the mass fraction of LiTFSI is 15% and the mass fraction of LATP is 0.5%.
Step 2, uniformly coating the polymer slurry prepared in the step 1 on one side of a double-layer PP/PE diaphragm, and drying at 60 ℃ for 5 hours to form a film; and (3) uniformly coating the polymer slurry prepared in the step (1) on the other side of the double-layer PP/PE diaphragm, and drying at 60 ℃ for 19h to form a film, thus obtaining the commercial diaphragm-based sandwich-structure polymer composite solid electrolyte film of the target product.
Comparative example 5
In this comparative example, a single polymer composite solid electrolyte membrane was prepared by the following steps:
step 1, dissolving PPC, LiTFSI and LATP in NMP under the condition of water bath at 45 ℃ to obtain uniform polymer slurry, wherein the mass fraction of PPC is 5%, the mass fraction of LiTFSI is 15% and the mass fraction of LATP is 0.5%.
And 2, uniformly coating the polymer slurry obtained in the step 1 on a glass plate, and drying at 60 ℃ for 24 hours to form a membrane, thereby obtaining the PPC/LATP polymer solid electrolyte membrane.
Example 6
In this example, a commercial polymer composite solid electrolyte membrane with a membrane-based sandwich structure was prepared as follows:
step 1, under the condition of water bath at 45 ℃, PMMA and LiNO are mixed3And LLZO in NMP to give a uniform polymer slurry in which PMMA is 20% by mass and LiNO is present3The mass fraction of (A) is 5% and the mass fraction of LLZO is 2%.
Step 2, uniformly coating the polymer slurry prepared in the step 1 on one side of a double-layer PP/PP diaphragm, and drying at 60 ℃ for 5 hours to form a film; and (3) uniformly coating the polymer slurry prepared in the step (1) on the other side of the double-layer PP/PP diaphragm, and drying for 19 hours at 60 ℃ to form a film, thus obtaining the commercial diaphragm-based sandwich-structure polymer composite solid electrolyte film of the target product.
Comparative example 6
In this comparative example, a single polymer composite solid electrolyte membrane was prepared by the following steps:
step 1, under the condition of water bath at 45 ℃, PMMA and LiNO are mixed3And LLZO is dissolved in NMP to obtain uniform polymer slurry, wherein the mass fraction of PMMA is 20 percent,LiNO3The mass fraction of (A) is 5% and the mass fraction of LLZO is 2%.
And 2, uniformly coating the polymer slurry obtained in the step 1 on a glass plate, and drying at 60 ℃ for 24 hours to form a film, thereby obtaining the PMMA/LLZO polymer solid electrolyte film.
Example 7
In this example, a commercial polymer composite solid electrolyte membrane with a membrane-based sandwich structure was prepared as follows:
step 1, under the condition of water bath at 45 ℃, PEG and LiBO are mixed3And Li6PS5Dissolving Cl in ACN to obtain uniform polymer slurry, wherein the mass fraction of PEG is 15%, and LiBO3Is 10% by mass, Li6PS5The mass fraction of Cl was 1.5%.
Step 2, uniformly coating the polymer slurry prepared in the step 1 on one side of the PE diaphragm, and drying at 60 ℃ for 5 hours to form a film; and (3) uniformly coating the polymer slurry prepared in the step (1) on the other side of the PE diaphragm, and drying at 60 ℃ for 19h to form a film, thus obtaining the commercial diaphragm-based sandwich-structured polymer composite solid electrolyte film of the target product.
Comparative example 7
In this comparative example, a single polymer composite solid electrolyte membrane was prepared by the following steps:
step 1, under the condition of water bath at 45 ℃, PEG and LiBO are mixed3And Li6PS5Dissolving Cl in ACN to obtain uniform polymer slurry, wherein the mass fraction of PEG is 15%, and LiBO3Is 10% by mass, Li6PS5The mass fraction of Cl was 1.5%.
Step 2, uniformly coating the polymer slurry obtained in the step 1 on a glass plate, and drying for 24 hours at the temperature of 60 ℃ to form a film to obtain PEG/Li6PS5A Cl polymer solid electrolyte membrane.
The polymer composite solid electrolyte membranes with sandwich structures prepared in the embodiments and the single polymer composite solid electrolyte membranes prepared in various proportions are respectively used as electrolytes, lithium iron phosphate is used as a positive electrode, a metal lithium sheet is used as a negative electrode, an experimental battery is assembled in an argon glove box, and the battery is subjected to constant voltage and constant current charge and discharge tests at the temperature of 25 ℃ and the current density of 0.3 ℃.
The polymer composite solid electrolyte membranes with sandwich structures prepared in the examples and the single polymer composite solid electrolyte membranes prepared in various proportions are respectively used as electrolytes, metal lithium sheets are used as positive and negative electrodes, a lithium symmetrical battery is assembled in an argon glove box, and the lithium stability test is carried out under the test conditions of 25 ℃ and 0.15mA/cm2The current density and the charging and discharging time of the battery were 30 min.
Fig. 1 is a cross-sectional scanning electron micrograph of the polymer composite solid electrolyte membrane with a sandwich structure prepared in example 1, which shows that the polymer composite solid electrolyte membrane has a sandwich structure, the thickness of the membrane is about 120 μm, and the thicknesses of the upper and lower polymer electrolyte layers are the same.
Fig. 2 is a graph showing cycle characteristics of a battery assembled by using as electrolytes the sandwich-structured polymer composite solid electrolyte membrane prepared in example 1 and the PVDF polymer solid electrolyte membrane prepared in comparative example 1, from which it can be seen that: the first discharge specific capacity of the polymer composite solid electrolyte membrane with the sandwich structure prepared in the embodiment 1 is 134mAh/g, the discharge specific capacity is still kept at 131mAh/g after 180 charge-discharge cycles, and the capacity retention rate is 97.76%; the PVDF polymer solid electrolyte membrane prepared in the comparative example 1 has the first discharge specific capacity of 125mAh/g, and after 60 charge-discharge cycles, the discharge specific capacity is 91mAh/g, and the capacity retention rate is 72.8%.
FIG. 3 is a graph showing the cycle characteristics of a battery assembled by using as electrolytes the polymer composite solid electrolyte membrane having a sandwich structure prepared in example 2 and the PVDF/LLZTO polymer solid electrolyte membrane prepared in comparative example 2, from which it can be seen that: the first discharge specific capacity of the polymer composite solid electrolyte membrane with the sandwich structure prepared in the embodiment 2 is 146mAh/g, the discharge specific capacity is still maintained at 150mAh/g after 200 charge-discharge cycles, and the capacity retention rate is 100%; the PVDF/LLZTO polymer solid electrolyte membrane prepared in comparative example 2 has a first discharge specific capacity of 142mAh/g, and after 200 charge-discharge cycles, the discharge specific capacity is 80mAh/g, and the capacity retention rate is 56.3%.
FIG. 4 is prepared as in example 1The lithium symmetrical cell assembled by using the polymer composite solid electrolyte membrane with sandwich structure and the PVDF polymer solid electrolyte membrane prepared in the comparative example 1 as the electrolyte is 0.15mA/cm2Constant current cycle plot at current density, as can be seen: the sandwich-structured polymer composite solid electrolyte membrane prepared in example 1 was short-circuited after 799 hours of cycle, while the PVDF polymer solid electrolyte membrane prepared in comparative example 1 was short-circuited after 49 hours of cycle.
FIG. 5 is a stress-strain diagram of the sandwich structure polymer composite solid electrolyte membrane prepared in example 1 and the PVDF polymer solid electrolyte membrane prepared in comparative example 1 at a tensile rate of 10mm/min, as can be seen from the graphs: the stress of the sandwich structure polymer composite solid electrolyte membrane prepared in example 1 was 7.05Mpa, while that of the PVDF polymer solid electrolyte membrane prepared in comparative example 1 was 5.69 Mpa.
Through tests, the polymer composite solid electrolytes with the sandwich structure prepared in other examples have excellent room-temperature cycling stability, lithium stability and mechanical property compared with a single polymer solid electrolyte membrane.
The above description is only exemplary of the present invention and should not be taken as limiting the invention, and any modifications, equivalents, improvements, etc. made within the spirit and principle of the present invention should be included in the scope of the present invention.

Claims (10)

1.商用隔膜基三明治结构聚合物复合固态电解质膜，其特征在于：所述聚合物复合固态电解质膜截面呈三明治结构，是在商用隔膜的两侧设置有聚合物层；所述聚合物层是通过涂布聚合物浆料并烘干而形成。1. A commercial diaphragm-based sandwich structure polymer composite solid electrolyte membrane is characterized in that: the cross section of the polymer composite solid electrolyte membrane is a sandwich structure, and a polymer layer is provided on both sides of the commercial diaphragm; the polymer layer is It is formed by coating a polymer slurry and drying it. 2.根据权利要求1所述的商用隔膜基三明治结构聚合物复合固态电解质膜，其特征在于：在40～65℃水浴条件下，将聚合物基体、锂盐和无机填料均匀溶解或分散于极性溶剂中，即获得所述聚合物浆料。2 . The commercial diaphragm-based sandwich structure polymer composite solid electrolyte membrane according to claim 1 , wherein the polymer matrix, lithium salt and inorganic filler are uniformly dissolved or dispersed in the electrode under the condition of 40-65° C. water bath. 3 . In the solvent, the polymer slurry is obtained. 3.根据权利要求2所述的商用隔膜基三明治结构聚合物复合固态电解质膜，其特征在于：所述聚合物基体为聚环氧乙烷、聚偏氟乙烯、聚偏氟乙烯-co-六氟丙烯、聚甲基丙烯酸甲酯、聚丙烯腈、聚乙二醇、聚乙烯醇、聚氯乙烯和聚碳酸丙烯酯中的至少一种。3. The commercial diaphragm-based sandwich structure polymer composite solid electrolyte membrane according to claim 2, wherein the polymer matrix is polyethylene oxide, polyvinylidene fluoride, polyvinylidene fluoride-co-hexa At least one of fluoropropylene, polymethyl methacrylate, polyacrylonitrile, polyethylene glycol, polyvinyl alcohol, polyvinyl chloride and polypropylene carbonate. 4.根据权利要求2所述的商用隔膜基三明治结构聚合物复合固态电解质膜，其特征在于：所述锂盐为高氯酸锂、双三氟甲基磺酰亚胺锂、双氟磺酰亚胺锂、硝酸锂、硼酸锂和氯化锂中的至少一种。4 . The commercial diaphragm-based sandwich structure polymer composite solid-state electrolyte membrane according to claim 2 , wherein the lithium salt is lithium perchlorate, lithium bistrifluoromethanesulfonimide, and bisfluorosulfonyl At least one of lithium imide, lithium nitrate, lithium borate and lithium chloride. 5.根据权利要求2所述的商用隔膜基三明治结构聚合物复合固态电解质膜，其特征在于：所述无机填料为SiO2、Al2O3、TiO2、ZnO、Li0.3La0.557TiO3、Li1.3Al0.3Ti1.7(PO4)3、Li7La3Zr2O12、Li6PS5Cl和Li6.4La3Zr1.4Ta0.6O12中的至少一种。5 . The commercial diaphragm-based sandwich structure polymer composite solid electrolyte membrane according to claim 2 , wherein the inorganic filler is SiO 2 , Al 2 O 3 , TiO 2 , ZnO, Li 0.3 La 0.557 TiO 3 , At least one of Li 1.3 Al 0.3 Ti 1.7 (PO 4 ) 3 , Li 7 La 3 Zr 2 O 12 , Li 6 PS 5 Cl and Li 6.4 La 3 Zr 1.4 Ta 0.6 O 12 . 6.根据权利要求2所述的商用隔膜基三明治结构聚合物复合固态电解质膜，其特征在于：所述极性溶剂为N,N-二甲基甲酰胺、N-甲基吡咯烷酮、无水乙腈中的至少一种。6. The commercial diaphragm-based sandwich structure polymer composite solid electrolyte membrane according to claim 2, wherein the polar solvent is N,N-dimethylformamide, N-methylpyrrolidone, anhydrous acetonitrile at least one of them. 7.根据权利要求1或2所述的商用隔膜基三明治结构聚合物复合固态电解质膜，其特征在于：所述商用隔膜为PE隔膜、PP隔膜、陶瓷涂布PE隔膜、陶瓷涂布PP隔膜、双层PP/PP隔膜、双层PP/PE隔膜和三层PP/PE/PP隔膜中的至少一种。7. The commercial diaphragm-based sandwich structure polymer composite solid electrolyte membrane according to claim 1 or 2, wherein the commercial diaphragm is a PE diaphragm, a PP diaphragm, a ceramic-coated PE diaphragm, a ceramic-coated PP diaphragm, At least one of a double-layer PP/PP membrane, a double-layer PP/PE membrane, and a triple-layer PP/PE/PP membrane. 8.根据权利要求2所述的商用隔膜基三明治结构聚合物复合固态电解质膜，其特征在于：在所述聚合物浆料中，聚合物基体的质量分数为5-20％，锂盐的质量分数为3-20％，无机填料的质量分数为0-10％。8 . The commercial diaphragm-based sandwich structure polymer composite solid electrolyte membrane according to claim 2 , wherein in the polymer slurry, the mass fraction of the polymer matrix is 5-20%, and the mass fraction of the lithium salt is 5-20%. 9 . The fraction is 3-20%, and the mass fraction of inorganic filler is 0-10%. 9.一种权利要求1～8中任意一项所述商用隔膜基三明治结构聚合物复合固态电解质膜的制备方法，其特征在于：9 . A preparation method of the commercial diaphragm-based sandwich structure polymer composite solid electrolyte membrane according to any one of claims 1 to 8, characterized in that: 步骤1、在40～65℃水浴条件下，将聚合物基体、锂盐和无机填料均匀溶解或分散于极性溶剂中，获得聚合物浆料；Step 1. Under the condition of water bath at 40～65℃, the polymer matrix, lithium salt and inorganic filler are uniformly dissolved or dispersed in polar solvent to obtain polymer slurry; 步骤2、在商用隔膜的一侧均匀涂布所述聚合物浆料并烘干成膜；再在商用隔膜的另一侧均匀涂布所述聚合物浆料并烘干成膜，即获得目标产品商用隔膜基三明治结构聚合物复合固态电解质膜。Step 2: Evenly coat the polymer slurry on one side of the commercial separator and dry to form a film; then evenly coat the polymer slurry on the other side of the commercial separator and dry to form a film, that is, the target is obtained Products Commercial separator-based sandwich structure polymer composite solid electrolyte membrane. 10.根据权利要求9所述的制备方法，其特征在于：步骤2中，第一次烘干是置于40～100℃真空烘箱中干燥2～7h，第二次烘干是置于40～100℃真空烘箱中干燥17～22h。10. The preparation method according to claim 9, characterized in that: in step 2, drying for the first time is drying in a vacuum oven at 40-100°C for 2-7 hours, and drying for the second time is drying at 40-100°C. Dry in a vacuum oven at 100°C for 17-22h.
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