CN111370760B - Composite solid electrolyte with wide electrochemical window and preparation method thereof - Google Patents
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Abstract
The invention relates to the field of electrochemical energy storage, in particular to a wide electrochemical window composite solid electrolyte and a preparation method thereof. The composite solid electrolyte comprises polyacrylonitrile, lithium salt, ceramic filler and protective layer material, and the preparation method comprises the following steps: firstly, preparing precursor slurry of the composite electrolyte by ball milling or heating and stirring; then, coating the slurry on a clean glass plate by adopting a tape casting method, and drying to obtain the PAN-based composite solid electrolyte; and finally, preparing protective layer slurry, uniformly coating the protective layer slurry on one surface of the PAN-based composite solid electrolyte by a spin coating method or a tape casting forming method, and drying to obtain the composite solid electrolyte with the wide electrochemical window. The composite solid electrolyte of the invention has wide electrochemical window (0-4.5V vs. Li/Li) + ) The lithium ion battery has the advantages of thin thickness (5-300 mu m), good flexibility, simple preparation method and the like, and is suitable for the fields of lithium ion batteries, flow batteries and the like.
Description
Technical Field
The invention relates to the field of electrochemical energy storage, in particular to a wide electrochemical window composite solid electrolyte and a preparation method thereof.
Background
A new generation of batteries with high energy density and high safety is a key for developing portable electronic products and electric automobiles, and recently has become an important research point in academia and industry. Lithium metal has extremely high energy density and most negative potential, and is known as a crown in the negative electrode material. In addition, the traditional lithium ion battery adopts lithium iron phosphate as an anode active material, and the potential and the energy density of the lithium iron phosphate are low, so that the requirement of the current market on a high-energy-density battery can not be met. The lithium metal cathode is adopted to replace the traditional carbon material cathode, the high-voltage ternary cathode is adopted to replace the lithium iron phosphate cathode, and the scheme for realizing the high-energy-density battery is the most potential at present. On the other hand, the traditional lithium ion battery uses flammable liquid electrolyte, and has serious potential safety hazard. The use of solid electrolytes instead of conventional liquid electrolytes can effectively solve this problem. And since the solid electrolyte generally has a high shear modulus, it can theoretically block the growth of lithium metal dendrites, and thus has the potential to put a lithium metal anode into practical use.
Although having many advantages, the current solid electrolyte is generally narrow in electrochemical window and cannot be simultaneously applied to a lithium metal negative electrode and a high-voltage ternary positive electrode. For example, oxide solid electrolyte perovskite type LLTO and Nasicon type LAGP have excellent cathode oxidation resistance, but are reduced by lithium metal, and cannot be adapted to lithium metal negative electrodes. As another example, polyethylene oxide (PEO) solid electrolyte has good compatibility with lithium metal, but the positive electrode has poor oxidation resistance, and is not suitable for a ternary battery.
Therefore, it is necessary to develop a solid electrolyte having a wide electrochemical window, thereby achieving a lithium metal ternary battery with high energy density and high safety.
Disclosure of Invention
The invention aims to provide a composite solid electrolyte with a wide electrochemical window and a preparation method thereof, wherein the composite solid electrolyte has a wide electrochemical window (0-4.5 Vvs. Li/Li + ) Thin thickness (5-300 μm) and excellent flexibility. The preparation process is simple and easy to control, has strong operability and is suitable for large-scale production.
In order to achieve the above purpose, the present invention proposes the following technical solutions:
the composite solid electrolyte with a wide electrochemical window comprises polyacrylonitrile, lithium salt, ceramic filler and protective layer material, wherein:
the ceramic filler is an inorganic nonmetallic material which does not conduct electrons, the protective layer material comprises an adhesive and a solid material which is contacted with lithium metal stably, the mass ratio of polyacrylonitrile to lithium salt is 1:0.001-1:10, the mass ratio of polyacrylonitrile to the ceramic filler is 1:20-1:0.01, and the mass ratio of polyacrylonitrile to the protective layer material is 1:1-1:0.0001; in the protective layer material, the mass ratio of the adhesive to the solid material which is stable in contact with lithium metal is 1:20-1:0.1.
The wide electrochemical window composite solid electrolyte has a wide electrochemical window of 0-4.5 Vvs. Li/Li + 。
The ceramic filler used in the composite solid electrolyte is boron nitride or zirconium oxide.
The lithium salt used in the composite solid electrolyte is lithium perchlorate or lithium bistrifluoromethane sulfonyl imide.
In the protective layer material of the composite solid electrolyte, the adhesive is polyvinylidene fluoride or polyacrylic acid, and the solid material is boron nitride or lithium fluoride.
The preparation method of the wide electrochemical window composite solid electrolyte comprises the following specific steps:
(1) Mixing polyacrylonitrile, lithium salt and ceramic filler according to a proportion, adding solvent N, N-dimethylformamide or dimethyl sulfoxide, and then ball milling or heating and stirring to obtain precursor slurry of the composite solid electrolyte, wherein the solid content of the precursor slurry is 5-95 wt%;
(2) Coating the slurry obtained in the step (1) on a clean glass plate by adopting a tape casting method, and heating and drying the glass plate in a vacuum oven to obtain the polyacrylonitrile-based composite solid electrolyte;
(3) And (3) dissolving the adhesive in a solvent N, N-dimethylformamide or dimethyl sulfoxide to form an adhesive solution, enabling the concentration of the adhesive in the solution to be 0.1-30wt%, dispersing the solid material for preparing the protective layer in the adhesive solution to form protective layer slurry, uniformly coating the protective layer slurry on one surface of the polyacrylonitrile-based composite solid electrolyte obtained in the step (2), and drying to obtain the composite solid electrolyte with the wide electrochemical window.
In the step (3), the protective layer slurry is coated on the surface of the polyacrylonitrile-based composite solid electrolyte by adopting a spin coating method or a tape casting method.
In the preparation method of the wide electrochemical window composite solid electrolyte, in the step (3), a spin coating method means: and a coating method for uniformly spreading the sol, solution or suspension on the surface of the substrate by using centrifugal force generated by rotation.
In the preparation method of the wide electrochemical window composite solid electrolyte, in the steps (2) and (3), the tape casting method refers to: the precursor slurry is first poured from the container, scraped and coated on the base band with scraper, dried and solidified to form the film of green belt, and the green belt is then punched or laminated according to the size and shape of the product.
In the step (2), the temperature of heating and drying in a vacuum oven is 30-150 ℃ for 1-36 h; in the step (3), the drying is carried out in a vacuum oven at 30-150 ℃ for 1-100 h.
The design idea of the invention is as follows:
the Polyacrylonitrile (PAN) -based solid electrolyte has good mechanical properties and positive electrode oxidation resistance, but the negative electrode has poor reduction resistance, so that the practicability is greatly limited. According to the invention, one surface of the PAN-based solid electrolyte has excellent cathode stability through simple surface modification, so that the wide electrochemical window composite solid electrolyte is obtained. Notably, the surface-modified slurry can dissolve a small amount of PAN during the drying process, thereby eliminating the interface between the protective layer and the PAN-based solid electrolyte. Thus, the wide electrochemical window composite solid electrolyte is a whole and has good mechanical properties.
The invention has the following advantages and beneficial effects:
1. the PAN-based composite solid electrolyte is prepared by a tape casting method, and then a protective layer is coated on the surface of the electrolyte by a spin coating method or a tape casting method, so that the composite solid electrolyte with the wide electrochemical window is successfully obtained. The composite solid electrolyte is applicable to a lithium metal negative electrode with low potential and a ternary positive electrode with high voltage, and has great application potential in the fields of lithium ion batteries, flow batteries and the like.
2. The preparation process is simple, quick and high in yield, and is suitable for large-scale production.
Drawings
Fig. 1 is a photograph of a wide electrochemical window composite solid electrolyte prepared in example 1. Wherein, (a) is a protective layer surface, (b) is a surface without a protective layer, and (c) is a curved pattern.
Fig. 2 is a Scanning Electron Microscope (SEM) image of the wide electrochemical window composite solid electrolyte prepared in example 1. Wherein (a) is the surface of the protective layer, (b) is the surface without the protective layer, and (c) is the cross section.
Fig. 3 is an Electrochemical Impedance Spectrum (EIS) of the wide electrochemical window composite solid electrolyte prepared in example 1. In the figure, the abscissa Z' represents the real part of the impedance (Ω) and the ordinate z″ represents the imaginary part of the impedance (Ω).
Fig. 4 is a Linear Sweep Voltammogram (LSV) of the wide electrochemical window composite solid electrolyte prepared in example 1.
Detailed Description
The present invention will be described more fully hereinafter in order to facilitate an understanding of the present invention. This invention may, however, be embodied in many different forms and should not be construed as limited to the embodiments set forth herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used herein in the description of the invention is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. The term "and/or" as used herein includes any and all combinations of one or more of the associated listed items.
In the specific implementation process, the components of the composite solid electrolyte with the wide electrochemical window are Polyacrylonitrile (PAN), lithium salt (for example, lithium perchlorate (LiClO) 4 ) Or lithium bis (trifluoromethanesulfonyl) imide (LiTFSI)), a ceramic filler (e.g.: boron Nitride (BN) and zirconium oxide (ZrO 2 ) Etc.), the former may be polyvinylidene fluoride (PVDF), polyacrylic acid (PAA), etc., and the latter may be Boron Nitride (BN), lithium fluoride (LiF), etc.), as well as a protective layer material (including a binder, which may be polyvinylidene fluoride (PVDF), polyacrylic acid (PAA), etc., and a solid material stable in contact with lithium metal, etc.), wherein: the mass ratio of the polyacrylonitrile to the lithium salt is 1:0.01-1:10 (preferably 1:0.3-1:1), the mass ratio of the polyacrylonitrile to the ceramic filler is 1:20-1:0.01 (preferably 1:4-1:0.05), and the mass ratio of the polyacrylonitrile to the protective layer material is 1:1-1:0.0001 (preferably 1:0.1-1:0.02); in the protective layer material, stickThe mass ratio between the binder and the solid material which is stable in contact with lithium metal is 1:20-1:0.1 (preferably 1:10-1:1). The preparation method of the wide electrochemical window composite solid electrolyte comprises the following steps: firstly, preparing precursor slurry of the composite electrolyte by ball milling or heating and stirring; then, coating the slurry on a clean glass plate by adopting a tape casting method, and drying to obtain the polyacrylonitrile-based composite solid electrolyte; and finally preparing protective layer slurry, uniformly coating the protective layer slurry on one surface of the obtained polyacrylonitrile-based composite solid electrolyte by a spin coating method or a tape casting forming method, and drying to obtain the composite solid electrolyte with the wide electrochemical window.
The present invention will be described in further detail below by way of examples and accompanying drawings.
Example 1:
the specific preparation process of the wide electrochemical window composite solid electrolyte in the embodiment is as follows:
0.1g of nano Boron Nitride (BN) is weighed and placed in 10ml of N, N-Dimethylformamide (DMF), ultrasonic treatment is carried out for 48 hours, and then the BN nano-sheets are obtained after centrifugation. Weighing 0.5g of Polyacrylonitrile (PAN), 0.25g of lithium perchlorate (LiClO) 4 ) Mixing with 0.05g BN nanosheets, adding 10ml of N, N-Dimethylformamide (DMF), heating and stirring at 80deg.C to obtain PAN and LiClO 4 And completely dissolving to obtain the precursor slurry of the composite solid electrolyte. And then the obtained slurry is coated on a clean glass plate by adopting a tape casting method, and is placed in a vacuum oven to be dried for 12 hours at 80 ℃ to obtain the PAN-BN composite solid electrolyte. Weighing 0.5-gBN nano-sheets and 0.06 polyvinylidene fluoride (PVDF), adding 10ml DMF, heating and stirring to dissolve PVDF, and obtaining the protective layer slurry. And finally, uniformly coating BN-PVDF slurry on the surface of the PAN-BN composite solid electrolyte by adopting a spin coating method, and preserving heat for 12 hours at 80 ℃ in a vacuum oven to obtain the wide electrochemical window composite solid electrolyte. In addition, the composite solid electrolyte can be cut into wafers of different sizes with a punch as needed.
The wide electrochemical window composite solid electrolyte of this example will be characterized in terms of structure and performance as follows:
FIG. 1 is a composite solid of the prepared wide electrochemical windowPhotographs of the electrolyte, and (a), (b) and (c) are the protective layer surface, the surface without the protective layer, and the bending pattern, respectively. As can be seen from fig. 1 (a) and (b), both surfaces of the composite electrolyte are uniform. As can be seen from fig. 1 (c), the composite electrolyte has excellent flexibility. Fig. 2 (a) is a surface of BN-PVDF protective layer, which is very dense and uniform, thus effectively avoiding PAN contact with lithium metal negative electrodes. It is worth mentioning that BN has a very high shear modulus and can effectively inhibit the growth of lithium metal dendrites. Fig. 2 (b) is a surface of the wide electrochemical window composite electrolyte without a protective layer, which is very uniform. FIG. 2 (c) is a cross-sectional view of the composite solid electrolyte, showing that the thickness of the BN-PVDF protective layer is about 1.5 μm, and the total thickness of the composite electrolyte (including the protective layer) is only about 13.5. Mu.m. More importantly, there was no clear boundary between the BN-PVDF protective layer and PAN-BN indicating that the wide electrochemical window composite electrolyte was a whole. This is mainly because the solvent of the overcoat slurry can also dissolve PAN, and thus a small amount of PAN substrate can be dissolved during the overcoat drying process, eliminating the interface between the two. FIG. 3 is an Electrochemical Impedance Spectroscopy (EIS) of a prepared wide electrochemical window composite solid electrolyte using a button cell fixture with a stainless steel sheet as a lithium ion blocking electrode, pressed into a button cell with the composite solid electrolyte sandwiched between two stainless steel sheets, and measured for ESI curves over a frequency range of 0.1 Hz-7 MHz. Based on the thickness of the composite solid, the area of the stainless steel sheet and the internal resistance of the composite solid electrolyte (obtained by fitting EIS data), the ion conductivity of the composite electrolyte was calculated to be 0.1mScm -1 . As can be seen from the linear sweep voltammogram of FIG. 4, the electrochemical window of the composite solid electrolyte is 0-4.5 Vvs. Li/Li + 。
Example 2:
the specific preparation process of the wide electrochemical window composite solid electrolyte in the embodiment is as follows:
weighing 0.5g of Polyacrylonitrile (PAN), 1.0g of lithium perchlorate (LiClO) 4 ) 0.1gZrO 2 Particles (particle size: 100 nm) were mixed, 15ml of dimethyl sulfoxide (DMSO) was added thereto, and the mixture was heated at 60 ℃Stirring to make PAN, liClO 4 And completely dissolving to obtain the precursor slurry of the composite solid electrolyte. Then the obtained slurry is coated on a clean glass plate by adopting a tape casting method, and is placed in a vacuum oven to be dried for 24 hours at 60 ℃ to obtain PAN-ZrO 2 Composite solid electrolyte. Then weighing 0.5-gBN nanometer sheet (diameter: 100 nm) and 0.01g polyvinylidene fluoride (PVDF), adding 15ml DMF, heating and stirring to dissolve PVDF, and obtaining the protective layer slurry. Finally, a tape casting method is adopted to uniformly coat BN-PVDF slurry on PAN-ZrO 2 And (3) preserving the heat of the surface of the composite solid electrolyte for 6 hours at 100 ℃ in a vacuum oven to obtain the composite solid electrolyte with the wide electrochemical window. In addition, the composite solid electrolyte can be cut into wafers of different sizes with a punch as needed.
Example 3:
the specific preparation process of the wide electrochemical window composite solid electrolyte in the embodiment is as follows:
0.1g of nano Boron Nitride (BN) is weighed and placed in 10ml of N, N-Dimethylformamide (DMF), ultrasonic treatment is carried out for 48 hours, and then the BN nano-sheet is obtained by centrifugation. Weighing 0.5g of Polyacrylonitrile (PAN), 0.6g of lithium bistrifluoro-methylsulfonylimide (LiTFSI) and 0.1g of obtained BN nanosheets, mixing, adding 30ml of dimethyl sulfoxide (DMSO), heating and stirring at 80 ℃ to obtain PAN and LiClO 4 Completely dissolved. And then the obtained slurry is coated on a clean glass plate by adopting a tape casting method, and is placed in a vacuum oven to be dried for 30 hours at 40 ℃ to obtain the PAN-BN composite solid electrolyte. Then 0.5g LiF particles (particle size: 1 um) and 0.3g polyvinylidene fluoride (PVDF) are weighed, 10ml DMSO is added, and PVDF is dissolved by heating and stirring, thus obtaining the protective layer slurry. And finally, uniformly coating LiF-PVDF slurry on the surface of the PAN-BN composite solid electrolyte by adopting a spin coating method, and preserving heat for 50 hours at 60 ℃ in a vacuum oven to obtain the wide electrochemical window composite solid electrolyte. In addition, the composite solid electrolyte can be cut into wafers of different sizes with a punch as needed.
Example 4:
the specific preparation process of the wide electrochemical window composite solid electrolyte in the embodiment is as follows:
weighing 0.5g of Polyacrylonitrile (PAN), 0.1g of lithium chloride (LiCl) and 0.2g of dioxideSilicon (SiO) 2 ) The nanoparticles were mixed, 30ml of N, N-Dimethylformamide (DMF) was added, and the mixture was heated and stirred at 30℃to completely dissolve PAN and LiCl. Then the obtained slurry is coated on a clean glass plate by adopting a tape casting method, and is placed in a vacuum oven to be dried for 36 hours at 30 ℃ to obtain PAN-SiO 2 Composite solid electrolyte. Then weighing 0.5g of BN nano-sheet prepared in example 1 and 0.3g of polyacrylic acid (PAA), adding 10ml of N-methylpyrrolidone (NMP), heating and stirring to dissolve the PAA, and obtaining the protective layer slurry. Finally, the BN-PAA sizing agent is uniformly coated on PAN-SiO by adopting a spin coating method 2 And (3) preserving the heat of the surface of the composite solid electrolyte for 12 hours at 80 ℃ in a vacuum oven to obtain the composite solid electrolyte with the wide electrochemical window. In addition, the composite solid electrolyte can be cut into wafers of different sizes with a punch as needed.
Example 5:
the specific preparation process of the wide electrochemical window composite solid electrolyte in the embodiment is as follows:
weighing 0.5g of Polyacrylonitrile (PAN), 1.0g of lithium perchlorate (LiClO) 4 ) 0.1g of tin oxide (SnO) 2 ) Mixing, adding 10ml N-methylpyrrolidone (NMP), heating and stirring at 50deg.C to obtain PAN and LiClO 4 Completely dissolved. Then the obtained slurry is coated on a clean glass plate by adopting a tape casting method, and is placed in a vacuum oven to be dried for 12 hours at 60 ℃ to obtain PAN-SnO 2 Composite solid electrolyte. Then weighing 0.5g gBN of the nano-sheet prepared in the example 1 and 0.1g of polyvinylidene fluoride (PVDF), adding 10ml of DMF, heating and stirring to dissolve PVDF, and obtaining the protective layer slurry. Finally, the BN-PVDF slurry is uniformly coated on PAN-SnO by adopting a spin coating method 2 And (3) preserving the heat of the surface of the composite solid electrolyte for 10 hours at 60 ℃ in a vacuum oven to obtain the composite solid electrolyte with the wide electrochemical window. In addition, the composite solid electrolyte can be cut into wafers of different sizes with a punch as needed.
The results of the examples show that the composite solid electrolyte of the invention has a wide electrochemical window (0 to 4.5Vvs. Li/Li) + ) The lithium ion battery has the advantages of thin thickness (5-300 mu m), good flexibility, simple preparation method and the like, and is suitable for the fields of lithium ion batteries, flow batteries and the like.
Claims (7)
1. The composite solid electrolyte with the wide electrochemical window is characterized by comprising the components of polyacrylonitrile, lithium salt, ceramic filler and protective layer material, wherein:
the mass ratio of the polyacrylonitrile to the lithium salt is 1:0.001-1:10, the mass ratio of the polyacrylonitrile to the ceramic filler is 1:20-1:0.01, and the mass ratio of the polyacrylonitrile to the protective layer material is 1:1-1:0.0001; the protective layer material comprises an adhesive and a solid material which is stable in contact with lithium metal, and the mass ratio of the adhesive to the solid material which is stable in contact with lithium metal is 1:20-1:0.1;
the ceramic filler is boron nitride or zirconium oxide, the lithium salt is lithium perchlorate or lithium bistrifluoro methanesulfonimide, the adhesive is polyvinylidene fluoride or polyacrylic acid, and the solid material is boron nitride or lithium fluoride;
the preparation method of the wide electrochemical window composite solid electrolyte comprises the following specific steps:
(1) Mixing polyacrylonitrile, lithium salt and ceramic filler according to a proportion, adding solvent N, N-dimethylformamide or dimethyl sulfoxide, and then ball milling or heating and stirring to obtain precursor slurry of the composite solid electrolyte, wherein the solid content of the precursor slurry is 5-95 wt%;
(2) Coating the precursor slurry of the composite solid electrolyte obtained in the step (1) on a clean glass plate by adopting a tape casting method, and heating and drying the glass plate in a vacuum oven to obtain the polyacrylonitrile-based composite solid electrolyte;
(3) And (3) dissolving the adhesive in a solvent N, N-dimethylformamide or dimethyl sulfoxide to form an adhesive solution, enabling the concentration of the adhesive in the solution to be 0.1-30wt%, dispersing the solid material for preparing the protective layer in the adhesive solution to form protective layer slurry, uniformly coating the protective layer slurry on one surface of the polyacrylonitrile-based composite solid electrolyte obtained in the step (2), and drying to obtain the composite solid electrolyte with the wide electrochemical window.
2. Wide electric power according to claim 1A chemical window composite solid electrolyte characterized in that the composite solid electrolyte has a wide electrochemical window of 0 to 4.5Vvs. Li/Li + 。
3. A method for preparing the wide electrochemical window composite solid electrolyte according to any one of claims 1 to 2, comprising the following specific steps:
(1) Mixing polyacrylonitrile, lithium salt and ceramic filler according to a proportion, adding solvent N, N-dimethylformamide or dimethyl sulfoxide, and then ball milling or heating and stirring to obtain precursor slurry of the composite solid electrolyte, wherein the solid content of the precursor slurry is 5-95 wt%;
(2) Coating the precursor slurry of the composite solid electrolyte obtained in the step (1) on a clean glass plate by adopting a tape casting method, and heating and drying the glass plate in a vacuum oven to obtain the polyacrylonitrile-based composite solid electrolyte;
(3) And (3) dissolving the adhesive in a solvent N, N-dimethylformamide or dimethyl sulfoxide to form an adhesive solution, enabling the concentration of the adhesive in the solution to be 0.1-30wt%, dispersing the solid material for preparing the protective layer in the adhesive solution to form protective layer slurry, uniformly coating the protective layer slurry on one surface of the polyacrylonitrile-based composite solid electrolyte obtained in the step (2), and drying to obtain the composite solid electrolyte with the wide electrochemical window.
4. The method for preparing a wide electrochemical window composite solid electrolyte according to claim 3, wherein in the step (3), a spin coating method or a tape casting method is used to coat the protective layer slurry on the surface of the polyacrylonitrile-based composite solid electrolyte.
5. The method for preparing a wide electrochemical window composite solid electrolyte according to claim 4, wherein in the step (3), spin coating means: and a coating method for uniformly spreading the sol, solution or suspension on the surface of the substrate by using centrifugal force generated by rotation.
6. The method for producing a wide electrochemical window composite solid electrolyte according to claim 4, wherein in the steps (2) and (3), the casting method means: the precursor slurry is first poured from the container, scraped and coated on the base band with scraper, dried and solidified to form the film of green belt, and the green belt is then punched or laminated according to the size and shape of the product.
7. The method for preparing a wide electrochemical window composite solid electrolyte according to claim 4, wherein in the step (2), the heating and drying temperature in a vacuum oven is 30-150 ℃ for 1-36 h; in the step (3), the drying is carried out in a vacuum oven at 30-150 ℃ for 1-100 h.
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