CN112909316B - 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 PDFInfo
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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
Technical Field
The invention belongs to the field of preparation of polymer solid electrolyte membranes of lithium ion batteries, 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). The inorganic filler is SiO 2 、Al 2 O 3 、TiO 2 、ZnO、Li 0.3 La 0.557 TiO 3 (LLTO)、Li 1.3 Al 0.3 Ti 1.7 (PO 4 ) 3 (LATP)、Li 7 La 3 Zr 2 O 12 (LLZO)、Li 6 PS 5 Cl and Li 6.4 La 3 Zr 1.4 Ta 0.6 O 12 (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 μm, the thickness of a commercial diaphragm layer is 20-40 μm, the thickness of a single-side polymer electrolyte layer is 5-100 μm, 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 the condition of a water bath at 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%.
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 to 7 hours in a vacuum oven at the temperature of between 40 and 100 ℃, and the second drying is carried out for 17 to 22 hours in the vacuum oven at the temperature of between 40 and 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 the polymer composite solid electrolyte with the diversified sandwich structure by uniformly coating lithium ion conduction type 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 mixed 4 Dissolving in DMF to obtain uniform PVDF/LiClO 4 Polymer paste, wherein the mass fraction of PVDF is 10%, liClO 4 Is 3.33 percent.
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 mixed 4 Dissolving in DMF to obtain uniform PVDF/LiClO 4 Polymer paste, wherein the mass fraction of PVDF is 10%, liClO 4 Is 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%.
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 SiO 2 Dissolving in ACN to obtain uniform polymer slurry, wherein the mass fraction of PEO is 9%, the mass fraction of LiTFSI is 6%, and SiO is 2 Is 2 percent.
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 SiO 2 Dissolving in ACN to obtain uniform polymer slurry, wherein the mass fraction of PEO is 9%, the mass fraction of LiTFSI is 6%, and SiO is 2 Is 2 percent.
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%.
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 baking 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%.
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 mixed 3 And LLZO in NMP to give a uniform polymer slurry with PMMA content of 20% by mass and LiNO content 3 The mass fraction of (A) is 5% and the mass fraction of LLZO is 2%.
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 mixed 3 And LLZO in NMP to give a uniform polymer slurry in which PMMA is 20% by mass and LiNO is present 3 The mass fraction of (2) and the mass fraction of LLZO were 5%.
And 2, uniformly coating the polymer slurry obtained in the step 1 on a glass plate, and baking for 24 hours at 60 ℃ to form a film, thereby obtaining the PMMA/LLZO polymer solid electrolyte film.
Example 7
In this example, the preparation steps of a commercial polymer composite solid electrolyte membrane with a membrane-based sandwich structure were as follows:
step 1, under the condition of water bath at 45 ℃, PEG and LiBO are mixed 3 And Li 6 PS 5 Dissolving Cl in ACN to obtain uniform polymer slurry, wherein the mass fraction of PEG is 15%, and LiBO 3 Is 10% by mass, li 6 PS 5 The mass fraction of Cl was 1.5%.
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 mixed 3 And Li 6 PS 5 Dissolving Cl in ACN to obtain uniform polymer slurry, wherein the mass fraction of PEG is 15%, and LiBO 3 Is 10% by mass, li 6 PS 5 The mass fraction of Cl was 1.5%.
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/cm 2 The current density and the charging and discharging time of the battery were 30min.
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 specific discharge capacity of 125mAh/g for the first time, and after 60 times of charge-discharge cycles, the specific discharge 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 kept at 150mAh/g after 200 times of 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 shows a lithium symmetrical cell at 0.15mA/cm, fabricated by assembling the polymer composite solid electrolyte membrane having a sandwich structure prepared in example 1 and the PVDF polymer solid electrolyte membrane prepared in comparative example 1 as electrolytes 2 Constant 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 sandwich structure polymer composite solid electrolyte membrane prepared in example 1 had a stress of 7.05Mpa, while the PVDF polymer solid electrolyte membrane prepared in comparative example 1 had a stress of 5.69Mpa.
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 (5)
1. The polymer composite solid electrolyte membrane with the commercial diaphragm-based sandwich structure is characterized in that: the cross section of the polymer composite solid electrolyte membrane is of a sandwich structure, and polymer layers are arranged on two sides of a commercial diaphragm; the polymer layer is formed by coating polymer slurry and drying;
the preparation method of the commercial membrane-based sandwich structure polymer composite solid electrolyte membrane comprises the following steps:
step 1, uniformly dissolving or dispersing a polymer matrix, lithium salt and an inorganic filler in a polar solvent under the condition of a water bath at 40-65 ℃ to obtain polymer slurry; the polar solvent is at least one of N, N-dimethylformamide, N-methylpyrrolidone and anhydrous acetonitrile; 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 the polymer slurry in a vacuum oven at 40-100 ℃ for 2-7 hours to form a film; and then the other side of the commercial diaphragm is evenly coated with the polymer slurry and is placed in a vacuum oven at the temperature of 40-100 ℃ for drying for 17-22 h to form a film, and the target product commercial diaphragm-based sandwich structure polymer composite solid electrolyte film is obtained.
2. The commercial membrane-based sandwich structured polymer composite solid electrolyte membrane according to claim 1, characterized in that: the polymer matrix is at least one of polyethylene oxide, polyvinylidene fluoride-co-hexafluoropropylene, polymethyl methacrylate, polyacrylonitrile, polyethylene glycol, polyvinyl alcohol, polyvinyl chloride and polypropylene carbonate.
3. The commercial membrane-based sandwich structured polymer composite solid electrolyte membrane according to claim 1, wherein: the lithium salt is at least one of lithium perchlorate, lithium bis (trifluoromethyl) sulfonyl imide, lithium bis (fluoro) sulfonyl imide, lithium nitrate, lithium borate and lithium chloride.
4. The commercial membrane-based sandwich structured polymer composite solid electrolyte membrane according to claim 1, characterized in that: the inorganic filler is SiO 2 、Al 2 O 3 、TiO 2 、ZnO、Li 0.3 La 0.557 TiO 3 、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 At least one of (1).
5. The commercial membrane-based sandwich structured polymer composite solid electrolyte membrane according to claim 1, wherein: the commercial diaphragm is at least one of a PE diaphragm, a 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.
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