CN111370760A - Wide electrochemical window composite solid electrolyte 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 a 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 molding 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 obtained PAN-based composite solid electrolyte by a spin-coating method or a tape-casting method, and drying to obtain the wide electrochemical window composite solid electrolyte. The composite solid electrolyte has wide electrochemical window (0-4.5V vs. Li/Li)+) Thin (5 to 300 μm) and flexibleGood toughness, 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
The new generation of high energy density and high safety battery is the key to the development of portable electronic products and electric vehicles, and has recently become the focus of research in academia and industry. Lithium metal has extremely high energy density and most negative potential, and is known as a crown in a negative electrode material. In addition, the traditional lithium ion battery adopts lithium iron phosphate as a positive active material, and the potential and energy density of the lithium iron phosphate are low, so that the requirement of the current market on a high-energy-density battery cannot be met. The lithium metal cathode is adopted to replace the traditional carbon material cathode, and the high-voltage ternary cathode is adopted to replace the lithium iron phosphate cathode, so that the scheme for realizing the high-energy density battery with the most potential at present is provided. On the other hand, the traditional lithium ion battery uses flammable liquid electrolyte, so that serious potential safety hazards exist. The solid electrolyte is adopted to replace the traditional liquid electrolyte, so that the problem can be effectively solved. Furthermore, since the solid electrolyte generally has a high shear modulus, it can theoretically block the growth of lithium metal dendrites, and thus has a potential for practical use of lithium metal negative electrodes.
Despite many advantages, current solid electrolytes are generally narrow in electrochemical window and cannot be applied to both lithium metal cathodes and high voltage ternary anodes. For example, oxide solid electrolyte perovskite-type LLTO and Nasicon-type LAGP have excellent anode oxidation resistance, but are reduced by lithium metal and cannot be adapted to lithium metal anodes. For another example, a polyethylene oxide (PEO) solid electrolyte has good compatibility with lithium metal, but the positive electrode has poor oxidation resistance, and cannot be applied to a ternary battery.
Therefore, it is necessary to develop a solid electrolyte having a wide electrochemical window, thereby realizing a lithium metal ternary battery having high energy density and high safety.
Disclosure of Invention
The invention aims to provide a wide electrochemical window composite solid electrolyte 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 purpose, the invention provides the following technical scheme:
the wide electrochemical window composite solid electrolyte comprises polyacrylonitrile, lithium salt, ceramic filler and a protective layer material, wherein the components of the composite solid electrolyte are as follows:
the ceramic filler is an inorganic non-conducting non-metallic material, the protective layer material comprises an adhesive and a solid material which is stably contacted with lithium metal, 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 stably contacted with the 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+。
The wide electrochemical window composite solid electrolyte is characterized in that a ceramic filler used in the composite solid electrolyte is boron nitride or zirconium oxide.
The lithium salt used in the wide electrochemical window composite solid electrolyte is lithium perchlorate or lithium bis (trifluoromethanesulfonyl) imide.
The wide electrochemical window composite solid electrolyte is characterized in that in a protective layer material of the composite solid electrolyte, a binder is polyvinylidene fluoride or polyacrylic acid, and a 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 ratio, adding a solvent N, N-dimethylformamide or dimethyl sulfoxide, and then carrying out 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 molding method, and placing the glass plate in a vacuum oven for heating and drying 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 0.1-30 wt%, dispersing a solid material for preparing a 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 wide electrochemical window composite solid electrolyte.
In the preparation method of the wide electrochemical window composite solid electrolyte, in the step (3), a spin coating method or a tape casting method is adopted to coat the protective layer slurry on the surface of the polyacrylonitrile-based composite solid electrolyte.
The preparation method of the wide electrochemical window composite solid electrolyte comprises the following steps of (3) spin coating: the coating method is characterized in that the sol, the solution or the suspension is uniformly spread on the surface of the substrate by utilizing the 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 method comprises pouring out the precursor slurry from a container, coating the precursor slurry on a base band by a scraper, drying, curing, peeling to form a film of the green band, and punching or laminating the green band according to the size and shape of the finished product.
The preparation method of the wide electrochemical window composite solid electrolyte comprises the following steps of (2), heating and drying in a vacuum oven at the temperature of 30-150 ℃ for 1-36 hours; in the step (3), the drying is carried out in a vacuum oven at the temperature of 30-150 ℃ for 1-100 h.
The design idea of the invention is as follows:
the Polyacrylonitrile (PAN) based solid electrolyte has good mechanical property and anode oxidation resistance, but the cathode reduction resistance is poor, so that the practicability is greatly limited. According to the invention, through simple surface modification, one surface of the PAN-based solid electrolyte has excellent cathode stability, so that the wide electrochemical window composite solid electrolyte is obtained. Notably, the surface modified slurry can dissolve a small amount of PAN during baking, thereby eliminating the interface between the protective layer and the PAN-based solid electrolyte. Therefore, 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 invention prepares the PAN-based composite solid electrolyte by a tape casting method, and then coats a protective layer on the surface of the electrolyte by adopting a spin coating method or a tape casting method, thereby successfully obtaining the wide electrochemical window composite solid electrolyte. The composite solid electrolyte can be suitable for a low-potential lithium metal cathode and a high-voltage ternary anode, and has great application potential in the fields of lithium ion batteries, flow batteries and the like.
2. The preparation process is simple, quick, high in yield and 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 the surface of the protective layer, (b) is the surface without the protective layer, and (c) is the 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 impedance (Ω), and the ordinate Z ″ represents the imaginary part of impedance (Ω).
Fig. 4 is a Linear Sweep Voltammogram (LSV) of the wide electrochemical window composite solid electrolyte prepared in example 1.
Detailed Description
In order that the invention may be more fully understood, reference will now be made to the following description. 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 in the description of the invention herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. As used herein, the term "and/or" includes any and all combinations of one or more of the associated listed items.
In the specific implementation process, the components of the wide electrochemical window composite solid electrolyte are Polyacrylonitrile (PAN) and lithium salt (such as lithium perchlorate (LiClO)4) Or lithium bis (trifluoromethanesulfonylimide) (LiTFSI)), a ceramic filler (e.g.: boron Nitride (BN), zirconium oxide (ZrO)2) Etc.) and protective layer materials (including a binder, which may be polyvinylidene fluoride (PVDF), polyacrylic acid (PAA), etc., and a solid material stable in contact with lithium metal, which may be Boron Nitride (BN), lithium fluoride (LiF), etc.), wherein: the mass ratio of polyacrylonitrile to lithium salt is 1: 0.01-1: 10 (preferably 1: 0.3-1: 1), the mass ratio of polyacrylonitrile to ceramic filler is 1: 20-1: 0.01 (preferably 1: 4-1: 0.05), and the mass ratio of polyacrylonitrile to protective layer material is 1: 1-1: 0.0001 (preferably 1: 0.1-1: 0.02); in the protective layer material, the mass ratio of the adhesive to the solid material which is stably contacted with the 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 molding 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 method, and drying to obtain the wide electrochemical window composite solid electrolyte.
The present invention will be described in further detail below by way of examples and figures.
Example 1:
the specific preparation process of the wide electrochemical window composite solid electrolyte of 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 centrifugation is carried out to obtain the peeled BN nano sheet. 0.5g Polyacrylonitrile (PAN) and 0.25g lithium perchlorate (LiClO) were weighed out4) And 0.05gBN nanosheet, and 10ml of N, N-dimethylformamide (b) was addedDMF), heating and stirring at 80 ℃ to ensure that PAN and LiClO4And completely dissolving to obtain the precursor slurry of the composite solid electrolyte. And coating the obtained slurry on a clean glass plate by adopting a tape casting method, and drying the glass plate in a vacuum oven at the temperature of 80 ℃ for 12 hours to obtain the PAN-BN composite solid electrolyte. Then 0.5gBN nanosheet and 0.06 polyvinylidene fluoride (PVDF) are weighed, 10ml of DMF is added, and heating and stirring are carried out to dissolve the PVDF, so that the protective layer slurry is obtained. And finally, uniformly coating the BN-PVDF slurry on the surface of the PAN-BN composite solid electrolyte by adopting a spin coating method, and preserving the heat for 12 hours in a vacuum oven at the temperature of 80 ℃ to obtain the wide electrochemical window composite solid electrolyte. Further, the composite solid electrolyte may be cut into wafers of different sizes by a punch as necessary.
The wide electrochemical window composite solid electrolyte of this example will be characterized in structure and performance as follows:
fig. 1 is a photograph of the prepared wide electrochemical window composite solid electrolyte, and (a), (b) and (c) are a surface of a protective layer, a surface without a protective layer, and a curved view, respectively. As can be seen from fig. 1(a), (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) shows the surface of a BN-PVDF protective layer, which is very dense and uniform, thus effectively avoiding PAN contact with a lithium metal negative electrode. It is worth mentioning that BN has a very high shear modulus, which effectively inhibits 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 BN-PVDF protective layer has a thickness of about 1.5 μm and the total thickness of the composite electrolyte (including the protective layer) is only about 13.5 μm. More importantly, there is no distinct boundary between the BN-PVDF protective layer and PAN-BN, indicating that the wide electrochemical window composite electrolyte is a whole. This is primarily because the solvent of the protective layer slurry also dissolves PAN and thus a small amount of PAN substrate during drying of the protective layer, thereby eliminating the interface between the two. FIG. 3 is the Electrochemical Impedance Spectroscopy (EIS) of the prepared wide electrochemical window composite solid electrolyte using button cell clipsThe composite solid electrolyte is sandwiched between two stainless steel sheets to form button cell, and ESI curve is measured in the frequency range of 0.1 Hz-7 MHz. According to the thickness of the composite solid, the area of the stainless steel sheet and the internal resistance of the composite solid electrolyte (obtained by EIS data fitting), the ionic conductivity of the composite electrolyte is 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+。
Example 2:
the specific preparation process of the wide electrochemical window composite solid electrolyte of the embodiment is as follows:
0.5g Polyacrylonitrile (PAN) and 1.0g lithium perchlorate (LiClO) were weighed out4) And 0.1g ZrO2Mixing the granules (particle diameter: 100nm), adding 15ml of dimethyl sulfoxide (DMSO), heating and stirring at 60 deg.C to obtain PAN and LiClO4And completely dissolving to obtain the precursor slurry of the composite solid electrolyte. Then coating the obtained slurry on a clean glass plate by adopting a tape casting method, and placing the glass plate in a vacuum oven to dry for 24 hours at the temperature of 60 ℃ to obtain PAN-ZrO2A composite solid electrolyte. Then 0.5gBN nano-sheet (diameter: 100nm) and 0.01g polyvinylidene fluoride (PVDF) are weighed, 15ml DMF is added, and the protective layer slurry is obtained by heating, stirring and dissolving PVDF. Finally, uniformly coating the BN-PVDF slurry on the PAN-ZrO by adopting a tape casting forming method2And (3) preserving the surface of the composite solid electrolyte in a vacuum oven at 100 ℃ for 6h to obtain the wide electrochemical window composite solid electrolyte. Further, the composite solid electrolyte may be cut into wafers of different sizes by a punch as necessary.
Example 3:
the specific preparation process of the wide electrochemical window composite solid electrolyte of the embodiment is as follows:
0.1g of nanometer Boron Nitride (BN) is weighed and placed in 10ml of N, N-Dimethylformamide (DMF), ultrasonic treatment is carried out for 48 hours, and then centrifugation is carried out to obtain the BN nanosheet. Weighing 0.5g of Polyacrylonitrile (PAN), 0.6g of lithium bistrifluoromethylsulfonylimide (LiTFSI) and 0.1g of the obtained BN nanosheet, mixing, adding 30ml of dimethyl sulfoxide (DMSO), heating at 80 ℃ and stirringMixing PAN and LiClO4And completely dissolving. And coating the obtained slurry on a clean glass plate by adopting a tape casting method, and drying the glass plate in a vacuum oven at 40 ℃ for 30h to obtain the PAN-BN composite solid electrolyte. Then 0.5g LiF particles (the particle size is about 1um) and 0.3g polyvinylidene fluoride (PVDF) are weighed, 10ml DMSO is added, and the PVDF is heated, stirred and dissolved to obtain the protective layer slurry. And finally, uniformly coating the LiF-PVDF slurry on the surface of the PAN-BN composite solid electrolyte by adopting a spin coating method, and preserving the heat for 50 hours in a vacuum oven at 60 ℃ to obtain the wide electrochemical window composite solid electrolyte. Further, the composite solid electrolyte may be cut into wafers of different sizes by a punch as necessary.
Example 4:
the specific preparation process of the wide electrochemical window composite solid electrolyte of the embodiment is as follows:
0.5g Polyacrylonitrile (PAN), 0.1g lithium chloride (LiCl) and 0.2g Silica (SiO) were weighed2) 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 coating the obtained slurry on a clean glass plate by adopting a tape casting method, and placing the glass plate in a vacuum oven to dry for 36 hours at the temperature of 30 ℃ to obtain PAN-SiO2A composite solid electrolyte. Then 0.5g of the BN nano-sheet prepared in example 1 and 0.3g of polyacrylic acid (PAA) are weighed, 10ml of N-methylpyrrolidone (NMP) is added, and the PAA is heated, stirred and dissolved to obtain the protective layer slurry. Finally, uniformly coating the BN-PAA slurry on the PAN-SiO by adopting a spin coating method2And (3) preserving the surface of the composite solid electrolyte in a vacuum oven at 80 ℃ for 12h to obtain the wide electrochemical window composite solid electrolyte. Further, the composite solid electrolyte may be cut into wafers of different sizes by a punch as necessary.
Example 5:
the specific preparation process of the wide electrochemical window composite solid electrolyte of the embodiment is as follows:
0.5g Polyacrylonitrile (PAN) and 1.0g lithium perchlorate (LiClO) were weighed out4) And 0.1g of tin oxide (SnO)2) Mixing, adding 10ml N-methylpyrrolidone (NMP), heating and stirring at 50 deg.C to make PAN and LiClO4And completely dissolving. Then the obtained slurry is mixedCoating the mixture on a clean glass plate by adopting a tape casting method, and drying the glass plate in a vacuum oven at 60 ℃ for 12h to obtain PAN-SnO2A composite solid electrolyte. Then 0.5gBN of the nano-sheet prepared in the embodiment 1 and 0.1g of polyvinylidene fluoride (PVDF) are weighed, 10ml of DMF is added, and the protective layer slurry is obtained by heating, stirring and dissolving the PVDF. Finally, uniformly coating the BN-PVDF slurry on PAN-SnO by adopting a spin coating method2And (3) preserving the surface of the composite solid electrolyte in a vacuum oven at 60 ℃ for 10h to obtain the wide electrochemical window composite solid electrolyte. Further, the composite solid electrolyte may be cut into wafers of different sizes by a punch as necessary.
The results of the examples show that the composite solid electrolyte has wide electrochemical window (0-4.5 Vvs. 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 (10)
1. The wide electrochemical window composite solid electrolyte is characterized in that the components of the composite solid electrolyte are polyacrylonitrile, lithium salt, ceramic filler and protective layer material, wherein:
the ceramic filler is an inorganic non-conducting non-metallic material, the protective layer material comprises an adhesive and a solid material which is stably contacted with lithium metal, 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 stably contacted with the lithium metal is 1: 20-1: 0.1.
2. The wide electrochemical window composite solid electrolyte of claim 1, wherein the composite solid electrolyte has a wide electrochemical window of 0 to 4.5V vs. Li/Li+。
3. The wide electrochemical window composite solid electrolyte according to claim 1, wherein the ceramic filler used in the composite solid electrolyte is boron nitride or zirconia.
4. The wide electrochemical window composite solid electrolyte according to claim 1, wherein the lithium salt used in the composite solid electrolyte is lithium perchlorate or lithium bis (trifluoromethanesulfonylimide).
5. The wide electrochemical window composite solid electrolyte as claimed in claim 1, wherein the protective layer of the composite solid electrolyte is made of polyvinylidene fluoride or polyacrylic acid as a binder, and boron nitride or lithium fluoride as a solid material.
6. A method for preparing the wide electrochemical window composite solid electrolyte according to any one of claims 1 to 5, comprising the following steps:
(1) mixing polyacrylonitrile, lithium salt and ceramic filler according to a ratio, adding a solvent N, N-dimethylformamide or dimethyl sulfoxide, and then carrying out 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 molding method, and placing the glass plate in a vacuum oven for heating and drying 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 0.1-30 wt%, dispersing a solid material for preparing a 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 wide electrochemical window composite solid electrolyte.
7. The method for preparing a wide electrochemical window composite solid electrolyte according to claim 6, wherein in the step (3), the slurry for the protective layer is coated on the surface of the polyacrylonitrile-based composite solid electrolyte by a spin coating method or a tape casting method.
8. The method for preparing a wide electrochemical window composite solid electrolyte according to claim 7, wherein in the step (3), the spin coating method means: the coating method is characterized in that the sol, the solution or the suspension is uniformly spread on the surface of the substrate by utilizing the centrifugal force generated by rotation.
9. The method for preparing a wide electrochemical window composite solid electrolyte according to claim 7, wherein in the steps (2) and (3), the tape casting method is: the method comprises pouring out the precursor slurry from a container, coating the precursor slurry on a base band by a scraper, drying, curing, peeling to form a film of the green band, and punching or laminating the green band according to the size and shape of the finished product.
10. The preparation method of the wide electrochemical window composite solid electrolyte according to claim 7, characterized in that in the step (2), the temperature for 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 the temperature of 30-150 ℃ for 1-100 h.
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| CN113764723A (en) * | 2021-09-08 | 2021-12-07 | 远景动力技术(江苏)有限公司 | Polymer electrolyte, polymer electrolyte layer, and all-solid-state lithium ion battery |
| CN114975856A (en) * | 2022-06-17 | 2022-08-30 | 珠海冠宇电池股份有限公司 | Electrode plate, battery and battery preparation method |
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