Super-hydrophobic material capable of conducting lithium ions as well as preparation method and application of super-hydrophobic material

Abstract

The invention relates to the technical field of battery materials, in particular to a super-hydrophobic material capable of conducting lithium ions and a preparation method and application of the super-hydrophobic material. When the preparation method of the super-hydrophobic material capable of conducting lithium ions is used for preparing a hydrophobic inorganic nano material, the preparation method comprises the following steps: providing inorganic nano particles; dispersing the inorganic nanoparticles in a first dispersant to form a first dispersion liquid containing the inorganic nanoparticles; and adding a fluorine-containing silane coupling agent and silicate ester into the first dispersion liquid, uniformly mixing and drying to form the hydrophobic inorganic nanoparticles. The material can reduce the possibility of contact between an attached matrix and water on the basis of transferring lithium ions, so that the matrix attached with the super-hydrophobic inorganic nano material capable of conducting lithium ions has better stability in air and can be conveniently stored in air.

Description

Technical Field

[0001] The present invention relates to the technical field of battery materials, and in particular to a super-hydrophobic material capable of conducting lithium ions, a preparation method thereof, and an application thereof in a sulfide electrolyte membrane. Background Art

[0002] In recent years, lithium-ion batteries have been widely used in consumer electronics, electric vehicles, large-scale energy storage and other fields. The electrolytes of lithium-ion batteries can be divided into organic liquid electrolytes and solid electrolytes. Organic liquid electrolytes have disadvantages such as flammability, volatility and poor heat resistance, so their development is restricted. Compared with organic electrolytes, all-solid-state batteries use non-flammable solid electrolytes instead of electrolytes and diaphragms, which fundamentally eliminates the safety hazards brought by liquid electrolytes, greatly improves the safety of batteries, and extends the service life of batteries.

[0003] At present, inorganic solid electrolytes mainly include oxide solid electrolytes, sulfide solid electrolytes and halide solid electrolytes. Among them, sulfide electrolytes have attracted more and more attention due to their good plasticity and high ionic conductivity. However, the electrochemical window of sulfide electrolytes is narrow and the electrochemical compatibility with positive electrode materials is poor. Among them, sulfide electrolytes are extremely sensitive to moisture in the air and can react with water to produce toxic gases. At the same time, after reacting with water, the composition, crystal structure and morphology of the sulfide electrolyte will also change, which will greatly attenuate the electrochemical properties such as ionic conductivity.

[0004] Due to the above properties of sulfide electrolytes, they are difficult to store in the air, which will increase the cost of material synthesis, processing and transportation, and battery preparation. Therefore, solving the air stability problem of sulfide electrolytes is of great significance to promote the development of all-solid-state batteries. Summary of the invention

[0005] The purpose of the present invention is to provide a super-hydrophobic material capable of conducting lithium ions, a preparation method and an application thereof. The material can reduce the possibility of contact between the attached substrate and water on the basis of transferring lithium ions, so that the substrate attached with the above-mentioned super-hydrophobic inorganic nanomaterial capable of conducting lithium ions has better stability in the air and can be stored in the air more conveniently.

[0006] In order to achieve the above object, the present invention adopts the following technical solution:

[0007] The invention provides a super hydrophobic material capable of conducting lithium ions, comprising organic polysilazane, hydrophobic inorganic nanoparticles and lithium ion conductor nanoparticles.

[0008] In some technical solutions of the present invention, the lithium ion conductor material is a polymer solid electrolyte, an inorganic solid electrolyte and a composite solid electrolyte, preferably a NASICON type oxide solid electrolyte.

[0009] In some technical solutions of the present invention, the super hydrophobic material capable of conducting lithium ions has a root mean square roughness greater than 30 nm and a surface energy less than 30 mJ / m 2 .

[0010] In some technical solutions of the present invention, the static contact angle of the superhydrophobic material capable of conducting lithium ions is greater than 130°, and the rolling angle is less than 10°.

[0011] In some technical solutions of the present invention, the static contact angle of the superhydrophobic material capable of conducting lithium ions is greater than 150°, and the rolling angle is less than 10°.

[0012] The present invention also provides a method for preparing the super-hydrophobic material capable of conducting lithium ions, the method comprising: providing hydrophobic inorganic nanoparticles, lithium ion conductor nanoparticles and organic polysilazane;

[0013] The hydrophobic inorganic nanoparticles, lithium ion conductor nanoparticles and organic polysilazane are mixed and dried.

[0014] In some technical solutions of the present invention, when preparing the hydrophobic inorganic nanomaterial, it includes the following steps: providing inorganic nanoparticles;

[0015] Dispersing the inorganic nanoparticles in a first dispersant to form a first dispersion containing the inorganic nanoparticles;

[0016] The fluorine-containing silane coupling agent and silicate are added to the first dispersion, mixed and dried to form hydrophobic inorganic nanoparticles.

[0017] In some technical schemes of the present invention, the preparation of the first dispersion includes reaction conditions of pH 8 to 12 and reaction at 20 to 80° C. for 6 to 24 hours; preferably, the reaction conditions are pH 8 and reaction at room temperature for 6 to 24 hours.

[0018] Furthermore, the pH may be adjusted with aqueous ammonia.

[0019] In some technical solutions of the present invention, the drying condition of the first dispersion is vacuum drying at 60-80° C. for 6-10 hours.

[0020] In some technical solutions of the present invention, the inorganic nanoparticles may be one or more of SiO2 nanoparticles, TiO2 nanoparticles, and montmorillonite; preferably, the inorganic nanoparticles may be SiO2 nanoparticles, TiO2 nanoparticles, and Al2O9Si3 nanoparticles.

[0021] In some technical solutions of the present invention, the mass ratio of the fluorine-containing silane coupling agent, the inorganic nanoparticles and the silicate is 0.1-2:1-5:1-5; preferably 0.1-1:1-2:1-2; more preferably 0.4:1:2.

[0022] In some technical solutions of the present invention, the first dispersant is an alcohol reagent; preferably at least one or more of methanol, ethanol, propanol, isopropanol, and ethylene glycol; more preferably ethanol.

[0023] In some technical solutions of the present invention, the mass fraction of the inorganic nanoparticles in the first dispersion is 10-50 wt %, preferably 20 wt %.

[0024] In some technical solutions of the present invention, the fluorine-containing silane coupling agent is one or more of tridecafluorooctyltrimethoxysilane, nonafluorohexyltrimethylsilane, pentafluorophenyltriethylsilane; preferably heptadecafluorodecyltriethoxysilane.

[0025] In some technical solutions of the present invention, the silicate is one or more of methyl orthosilicate, ethyl orthosilicate, and isopropyl orthosilicate; preferably isopropyl orthosilicate.

[0026] In some technical solutions of the present invention, the lithium ion conductor material is a polymer solid electrolyte, an inorganic solid electrolyte or a composite solid electrolyte, preferably a NASICON type oxide solid electrolyte containing lithium, and more preferably LATP.

[0027] Furthermore, the particle size of LATP is 500nm~2μm.

[0028] In some technical solutions of the present invention, during the step of mixing and drying the hydrophobic inorganic nanoparticles, the lithium ion conductor nanoparticles and the organic polysilazane, the method comprises:

[0029] Adding lithium ion conductor nanoparticles into a second dispersant for dispersion to form a second dispersion containing lithium ion conductor nanoparticles;

[0030] The hydrophobic inorganic nanoparticles and the organic polysilazane are added into the second dispersion, mixed and dried.

[0031] In some technical solutions of the present invention, the preparation of the second dispersion includes mixing at room temperature for 4 to 12 hours.

[0032] In some technical solutions of the present invention, the second dispersion is dried under vacuum at 80-120° C. for 4-24 hours; preferably, the second dispersion is dried under vacuum at 80° C. for 24 hours.

[0033] In some technical schemes of the present invention, the mass ratio of the organic polysilazane, the lithium ion conductor nanoparticles and the hydrophobic inorganic nanoparticles is 1-2:6-8:1-2; preferably 1-1.5:7-8:1-2; more preferably 1:8:1, 1:7:2 or 2:7:1.

[0034] In some technical solutions of the present invention, the second dispersant is ethanol and deionized water in a volume ratio of 8.5-9.5:1.5-0.5, preferably 9:1.

[0035] In some technical solutions of the present invention, the solid content of the second dispersion is 0.5-1.5%, preferably 1%.

[0036] In some technical solutions of the present invention, the hydrophobic inorganic nanoparticles and the organic polysilazane are added to the second dispersion liquid with a solid content of 30-50%.

[0037] The present invention further provides an application method of the above-mentioned super-hydrophobic material capable of conducting lithium ions, comprising the following steps:

[0038] Providing a super-hydrophobic material capable of conducting lithium ions, and adding the super-hydrophobic material to a third dispersant to form a third dispersion;

[0039] The third dispersion is applied to the surface of the substrate and dried.

[0040] In some technical solutions of the present invention, the third dispersion is dried in a vacuum drying oven at 80-120° C. for 6-24 hours; preferably, in a vacuum drying oven at 80° C. for 8 hours.

[0041] In some technical solutions of the present invention, the third dispersant may be at least one of solvents such as xylene, tetrahydrofuran, heptane, isopropanol, etc.; preferably xylene.

[0042] In some technical solutions of the present invention, the matrix may be a sulfide solid electrolyte.

[0043] In some technical solutions of the present invention, the dispersion may be cleaned before drying, such as by centrifugal cleaning or suction filtration cleaning.

[0044] In some technical solutions of the present invention, the mixing and dispersing method specifically includes: one or more methods of magnetic stirring, vortex oscillation, ultrasonic oscillation, and mechanical stirring.

[0045] In some technical solutions of the present invention, the organopolysilazane contains The polymer of the structural unit has a main chain of Si~N bond, and the side chain substituents R1, R2, and R3 are independently one or more of hydrogen, alkyl, alkenyl or alkynyl. The Si-H, NH, and Si-N bonds contained in the structure are easily hydrolyzed with water. The organic group polysilazane is easy to hydrolyze with water vapor in the air and is converted into an extremely stable and dense Si~O film, which can effectively block gases such as water vapor and oxygen. The pH value of the hydrolysis environment will affect the degree of hydrolysis of the Si~N bond. The generated silicon dioxide film can effectively block water vapor and oxygen. At the same time, the polysilazane macromolecule is anchored on the surface of the sulfide solid electrolyte by covalent bonding.

[0046] The present invention can form a surface micro-nano composite structure on the surface of the coating by introducing hydrophobic inorganic nanoparticles, thereby improving the hydrophobicity of the coating and the air stability of the protected material.

[0047] The preparation process of the super-hydrophobic material coating capable of conducting lithium ions of the present invention is simple, and deposition methods such as dipping, spraying and scraping are adopted, which is conducive to simplifying the process and the preparation process. DETAILED DESCRIPTION

[0048] Definition and explanation:

[0049] In the present disclosure, a numerical range expressed using "to" means a range including the numerical values ​​described before and after "to" as a minimum value and a maximum value, respectively.

[0050] In the numerical ranges recorded in stages in the present disclosure, the upper limit or lower limit recorded in a certain numerical range can be replaced by the upper limit or lower limit of the numerical range recorded in other stages. In the numerical ranges recorded in the present disclosure, the upper limit or lower limit recorded in a certain numerical range can be replaced by the value shown in the embodiment.

[0051] Unless the context clearly indicates otherwise, when used in this specification, the terms “comprises”, “comprising” and “includes” specify the presence of stated elements but do not exclude the presence or addition of one or more other elements.

[0052] In some technical solutions of the present invention, unless otherwise specified, the "conductor material" or "solid electrolyte" includes polymer solid electrolytes, inorganic solid electrolytes and composite solid electrolytes. Furthermore, inorganic solid electrolytes can be divided into crystalline solid electrolytes and amorphous solid electrolytes according to their crystal structure. Crystalline solid electrolytes include NASICON-type, perovskite-type, garnet-type solid electrolytes in oxides and Li-ion-based solid electrolytes in sulfides. 10 GeP2S 12 (LGPS), etc. The specific NASICON-type oxide solid electrolytes include Li 1.4 Al 0.4 Ti 1.6 (PO4)3(LATP), etc.; and amorphous solid electrolytes include LiPON-type solid electrolytes in oxides and glass or glass-ceramic electrolytes such as Li2S~P2S5 in sulfides.

[0053] In some technical solutions of the present invention, unless otherwise specified, the method of "stirring" or "mixing" to make the various mixtures fully and evenly dispersed includes: one or more methods of magnetic stirring, ultrasonic vibration, and mechanical stirring.

[0054] In some technical solutions of the present invention, unless otherwise specified, the coating method specifically includes one of a dipping method, a spraying method and a scraping method.

[0055] The technical solutions in the embodiments of the present application will be described clearly and completely below in conjunction with the embodiments of the present application. Obviously, the described embodiments are only a part of the embodiments of the present application, rather than all of the embodiments. Based on the embodiments in the present application, all other embodiments obtained by those skilled in the art without creative work are within the scope of protection of the present application.

[0056] The present invention discloses a super-hydrophobic material capable of conducting lithium ions, a preparation method and an application of the super-hydrophobic material capable of conducting lithium ions. The material can reduce the possibility of contact between an attached substrate and water on the basis of transferring lithium ions, so that the substrate attached with the super-hydrophobic inorganic nanomaterial capable of conducting lithium ions has better stability in the air and can be stored in the air more conveniently.

[0057] A method for preparing a super-hydrophobic material capable of conducting lithium ions provided in an embodiment of the present invention comprises the following steps:

[0058] S11: providing hydrophobic inorganic nanoparticles, lithium ion conductor nanoparticles and organic polysilazane;

[0059] In this embodiment, the hydrophobic inorganic nanoparticles can be prepared by the following method:

[0060] S111: providing inorganic nanoparticles;

[0061] In this step, the inorganic nanoparticles may be one or more of SiO2 nanoparticles, TiO2 nanoparticles, and montmorillonite.

[0062] S112: dispersing the inorganic nanoparticles in a first dispersant to form a first dispersion containing the inorganic nanoparticles;

[0063] In this step, the first dispersant may be an alcohol solvent, such as at least one or more of methanol, ethanol, propanol, isopropanol, ethylene glycol and the like.

[0064] After the inorganic nanoparticles are added to the first dispersant, the inorganic nanoparticles can be dispersed by ultrasonic dispersion, mechanical dispersion, etc. to finally form a first dispersion with a mass fraction of 10 to 50 wt%, preferably 15 to 25 wt%.

[0065] S113: adding a fluorine-containing silane coupling agent and a silicate into the first dispersion, mixing and drying the mixture to form hydrophobic inorganic nanoparticles.

[0066] In this embodiment, the mass ratio of the fluorine-containing silane coupling agent, the inorganic nanoparticles and the silicate is 0.1-2: 1-5: 1-5, preferably 0.3-0.5: 1.5-2.5: 1.5-2.5.

[0067] In this embodiment, the fluorine-containing silane coupling agent is one or more of tridecafluorooctyltrimethoxysilane, nonafluorohexyltrimethylsilane, and pentafluorophenyltriethylsilane; the silicate is one or more of methyl orthosilicate, ethyl orthosilicate, and isopropyl orthosilicate.

[0068] During the mixing, one or more methods including magnetic stirring, vortex oscillation, ultrasonic oscillation and mechanical stirring can be used to uniformly mix the fluorinated silane coupling agent, silicate and inorganic nanoparticle dispersion.

[0069] During the mixing, the pH of the mixed solution of the fluorinated silane coupling agent, silicate and inorganic nanoparticle dispersion can be adjusted to a pH of 8 to 12. Preferably, the mixed solution can be adjusted with ammonia water.

[0070] After mixing, the mixed solution of the fluorine-containing silane coupling agent, silicate and inorganic nanoparticle dispersion can be allowed to react at 20 to 80° C. for 6 to 24 hours to fully react.

[0071] Before drying, the mixed solution of the fluorinated silane coupling agent, silicate and inorganic nanoparticle dispersion may be cleaned, such as by centrifugal cleaning or suction filtration cleaning.

[0072] When drying is performed, the drying conditions are preferably vacuum drying at 60 to 80° C. for 6 to 10 hours.

[0073] In this embodiment, the inorganic nanoparticles are combined with silicate via a fluorine-containing silane coupling agent, so that the inorganic nanoparticles have better hydrophobicity.

[0074] In this embodiment, the organopolysilazane is The polymer of the structural unit has a main chain of Si-N bond; the organic group polysilazane is easily hydrolyzed with water vapor in the air and converted into an extremely stable and dense Si-O film that can effectively block gases such as water vapor and oxygen. The pH value of the hydrolysis environment will affect the degree of hydrolysis of the Si-N bond. 2、 R3 can be one or more of an alkyl group, an alkenyl group or an alkynyl group.

[0075] In this embodiment, the lithium ion conductor nanoparticles can be polymer solid electrolytes, inorganic solid electrolytes and composite solid electrolytes, preferably NASICON type oxide nanoscale solid electrolytes containing lithium elements. 1.4 Al 0.4 Ti 1.6 (PO4)3).

[0076] The size of the lithium ion conductor nanoparticles may be 500 nm to 2 μm.

[0077] S12: mixing and drying the hydrophobic inorganic nanoparticles, the lithium ion conductor nanoparticles and the organic polysilazane to obtain a super hydrophobic material capable of conducting lithium ions.

[0078] In this embodiment, the mass ratio of the organic polysilazane, the lithium ion conductor nanoparticles and the hydrophobic inorganic nanomaterial is 1-2:6-8:1-2, preferably 1:8:1, 1:7:2 or 2:7:1.

[0079] When mixing, the method comprises the following steps:

[0080] S121: adding lithium ion conductor nanoparticles into a second dispersant for dispersion to form a second dispersion containing lithium ion conductor nanoparticles;

[0081] In this embodiment, the second dispersant is preferably a mixture of ethanol and deionized water, and the volume ratio of ethanol to deionized water can be 8.5-9.5:1.5-0.5, preferably 9:1. In the second dispersion, the solid content of the lithium ion conductor nanoparticles is 0.5-1.5% by mass.

[0082] S122: adding hydrophobic inorganic nanoparticles and organic polysilazane into the second dispersion, mixing and drying the mixture to form a super hydrophobic material capable of conducting lithium ions.

[0083] In this embodiment, the mass ratio of the organic polysilazane, the lithium ion conductor nanoparticles and the hydrophobic inorganic nanoparticles is 1-2:6-8:1-2, preferably 1:8:1, 1:7:2 or 2:7:1. When the hydrophobic inorganic nanoparticles and the organic polysilazane are added to the second dispersion, the solid content of the entire mixed solution is 30-50% by mass. When mixing, the hydrophobic inorganic nanoparticles, the organic polysilazane and the second dispersion can be uniformly mixed by one or more of magnetic stirring, vortex oscillation, ultrasonic oscillation and mechanical stirring. When mixing, it can be mixed at room temperature, such as 25°C, for 4-12 hours.

[0084] Before drying, the mixture of the organopolysilazane, the lithium ion conductor nanoparticles and the second dispersion may be washed, such as by centrifugal washing or suction filtration washing.

[0085] When drying is performed, the drying conditions are preferably vacuum drying at 80 to 120° C. for 4 to 24 hours.

[0086] In this embodiment, organic polysilazane is combined with hydrophobic inorganic nanoparticles, and lithium ion conductor nanoparticles are filled between the organic polysilazane and the hydrophobic inorganic nanoparticles. Organic polysilazane is a polymer with a main chain structure of Si-N bonds, and its structure contains a large number of Si-H, NH, and Si-N bonds. When the super-hydrophobic material that can conduct lithium ions is attached to a substrate, such as the surface of a sulfide solid electrolyte, the side that contacts the air is easily hydrolyzed with water to form a silicon dioxide film. This film can effectively block water vapor and oxygen and prevent water from contacting the substrate. At the same time, the side released from the matrix will anchor the polysilazane macromolecules on the surface of the matrix in a covalently bonded manner, thereby ensuring the stability of the attachment; further, by introducing lithium ion conductor nanoparticles, the matrix can still have good ion conductivity when the material is attached to the surface of the matrix; further, by introducing hydrophobic inorganic nanoparticles, an organic polysilazane-hydrophobic inorganic nanoparticle micro-nano composite structure can be formed on the surface of the matrix, which, on the one hand, improves the hydrophobicity of the coating and the air stability of the protected material, and on the other hand, can more stably accommodate the lithium ion conductor nanoparticles, which is convenient for the lithium ion conductor nanoparticles to conduct ions.

[0087] The present invention also provides a super hydrophobic material capable of conducting lithium ions, the material comprising organic polysilazane, hydrophobic inorganic nanoparticles and lithium ion conductor nanoparticles.

[0088] More specifically, in this embodiment, the mass ratio of the organic polysilazane, the lithium ion conductor nanoparticles and the hydrophobic inorganic nanoparticles is 1-2:6-8:1-2, preferably 1:8:1, 1:7:2 or 2:7:1.

[0089] The super-hydrophobic material that can conduct lithium ions has a micro-nano rough structure with a root mean square roughness greater than 30nm. Its surface energy is less than 30mJ / m 2 .

[0090] The static contact angle of water of the superhydrophobic material capable of conducting lithium ions is greater than 130°, and the rolling angle is less than 10°; preferably, the static contact angle of water is greater than 150°.

[0091] The present invention also provides an application method of a super-hydrophobic material capable of conducting lithium ions, the method comprising the following steps:

[0092] S21: providing a super hydrophobic material capable of conducting lithium ions, and adding the super hydrophobic material to a third dispersant to form a third dispersion;

[0093] In this embodiment, the third dispersant may be at least one of solvents such as xylene, tetrahydrofuran, heptane, and isopropanol.

[0094] S22: applying the third dispersion onto the substrate surface and drying it.

[0095] In this embodiment, the coating method can be one of dipping, spraying and scraping. The drying condition is to dry in a vacuum drying oven at 80-120° C. for 6 to 24 hours.

[0096] The matrix may be a sulfide solid electrolyte.

[0097] The above solution is described in detail below with reference to a number of embodiments.

[0098] Embodiment 1:

[0099] 1. Ultrasonic dispersion of 1.0 g SiO2 nanoparticles in 4.0 g of anhydrous ethanol as a first dispersant to obtain a first dispersion with a mass fraction of 20 wt%; 0.4 g of heptadecafluorodecyltriethoxysilane and 2 g of isopropyl orthosilicate are added to the first dispersion, and its pH value is adjusted to 8 by adding ammonia water; the mixing temperature is room temperature, and the mixing time is 6 to 24 hours to obtain a hydrophobic SiO2 nanodispersion. After centrifugal washing or suction filtration washing of the hydrophobic SiO2 nanodispersion, the obtained sample is vacuum dried at 60 to 80°C for 6 to 10 hours to obtain hydrophobic SiO2 inorganic nanoparticles;

[0100] 2. Take an appropriate amount of lithium ion conductor nanoparticles LATP with a particle size range of 500nm to 2μm, mix and disperse them in a second dispersant of ethanol and deionized water (V:V=9:1), and stir rapidly at room temperature to obtain a second dispersion, wherein the solid content of the dispersion is 1%;

[0101] 3. Add organic polysilazane and hydrophobic SiO2 inorganic nanoparticles to the second dispersion, wherein the mass ratios of organic polysilazane, lithium ion conductor nanoparticles LATP and hydrophobic SiO2 inorganic nanoparticles are (1:8:1, 1:7:2, 2:7:1), respectively, and stir the dispersion magnetically at room temperature to obtain 3 uniform dispersions. Centrifuge each of the prepared dispersions, wash the obtained precipitate with anhydrous ethanol, and vacuum dry the washed precipitate at 80°C for 24 hours, thereby obtaining 3 super hydrophobic materials that can conduct lithium ions in different proportions;

[0102] 4. Dispersing different proportions of super-hydrophobic materials capable of conducting lithium ions in ultra-dry xylene, respectively, and preparing three third dispersions by magnetic stirring at room temperature and subsequent ultrasonic dispersion;

[0103] 5 . The coating was prepared on both sides of a 100 μm sulfide electrolyte membrane by using an immersion method. The sulfide electrolyte membrane was immersed in the third dispersion for 2 minutes and then taken out, and this process was repeated three times.

[0104] 6. The sulfide electrolyte membrane was placed in a vacuum drying oven at 80° C. for 8 hours to volatilize the xylene solvent, thereby obtaining three sulfide electrolyte membranes coated with super-hydrophobic materials capable of conducting lithium ions in different proportions.

[0105] The static contact angles of water of sulfide electrolyte membranes coated with three different proportions of superhydrophobic materials that can conduct lithium ions and untreated sulfide electrolyte membranes were tested using a contact angle meter; and the ability of sulfide electrolyte membranes coated with different proportions of superhydrophobic materials that can conduct lithium ions of sulfide electrolyte membranes was tested using AC impedance spectroscopy. The test results are shown in Tables 1-3.

[0106] Table 1 Electrolyte conductivity test results

[0107]

[0108]

[0109] It can be seen from the above data that in Example 1, compared with the untreated sulfide electrolyte membrane, the static contact angle of water of the sulfide electrolyte membrane coated with the superhydrophobic material that can conduct lithium ions is significantly increased, and it still has a certain ion conductivity.

[0110] Embodiment 2:

[0111] 1. Ultrasonic dispersion of 1.0 g TiO2 nanoparticles in a first dispersant of 4.0 g anhydrous ethanol to obtain a first dispersion with a mass fraction of 20 wt%; 0.4 g heptadecafluorodecyl triethoxysilane and 2 g isopropyl orthosilicate are added to the first dispersion, and its pH value is adjusted to 8 by adding ammonia water; the mixing temperature is room temperature, and the mixing time is 6 to 24 hours to obtain a hydrophobic TiO2 nanodispersion. After the hydrophobic TiO2 nanodispersion is centrifugally cleaned or filtered, the obtained sample is vacuum dried at 60 to 80°C for 6 to 10 hours to obtain hydrophobic TiO2 inorganic nanoparticles;

[0112] 2. Take an appropriate amount of lithium ion conductor nanoparticles LATP with a particle size range of 500nm to 2μm, mix and disperse them in a second dispersant of ethanol and deionized water (V:V=9:1), and stir rapidly at room temperature to obtain a second dispersion, wherein the solid content of the dispersion is 1%;

[0113] 3. Add organic polysilazane and hydrophobic TiO2 inorganic nanoparticles to the second dispersion, wherein the mass ratios of organic polysilazane, oxide solid electrolyte LATP and hydrophobic TiO2 inorganic nanoparticles are (1:8:1, 1:7:2, 2:7:1) respectively, and stir magnetically at room temperature to obtain 3 uniform dispersions. Centrifuge each of the prepared dispersions, wash the obtained precipitate with anhydrous ethanol, and vacuum dry the washed precipitate at 80°C for 24 hours, thereby obtaining 3 super hydrophobic materials that can conduct lithium ions in different proportions;

[0114] 4. Dispersing different proportions of super-hydrophobic materials capable of conducting lithium ions in ultra-dry xylene, respectively, and preparing three third dispersions by magnetic stirring at room temperature and subsequent ultrasonic dispersion;

[0115] 5. Prepare coatings on both sides of a 100 μm sulfide electrolyte membrane using a blade coating method, and use a blade to apply the third dispersion coating to both sides of the electrolyte membrane;

[0116] 6. The sulfide electrolyte membrane was placed in a vacuum drying oven at 80° C. for 8 hours to volatilize the xylene solvent, thereby obtaining three sulfide electrolyte membranes coated with super-hydrophobic materials capable of conducting lithium ions in different proportions.

[0117] Table 2 Electrolyte conductivity test results

[0118]

[0119] It can be seen from the above data that in Example 2, compared with the untreated sulfide electrolyte membrane, the static contact angle of water of the sulfide electrolyte membrane coated with the superhydrophobic material that can conduct lithium ions is significantly increased, and it still has a certain ion conductivity.

[0120] Embodiment 3:

[0121] 1. Ultrasonic dispersion of 1.0 g of Al2O9Si3 nanoparticles in 4.0 g of anhydrous ethanol as a first dispersant to obtain a first dispersion with a mass fraction of 20 wt%; 0.4 g of heptadecafluorodecyltriethoxysilane and 2 g of isopropyl orthosilicate are added to the first dispersion, and its pH value is adjusted to 8 by adding ammonia water; the mixing temperature is room temperature, and the mixing time is 6 to 24 hours to obtain a hydrophobic Al2O9Si3 nanodispersion. After the hydrophobic Al2O9Si3 nanodispersion is centrifugally cleaned or filtered, the obtained sample is vacuum dried at 60 to 80°C for 6 to 10 hours to obtain hydrophobic Al2O9Si3 inorganic nanoparticles;

[0122] 2. Take an appropriate amount of lithium ion conductor nanoparticles LATP with a particle size range of 500nm to 2μm, mix and disperse them in a second dispersant of ethanol and deionized water (V:V=9:1), and stir rapidly at room temperature to obtain a second dispersion, wherein the solid content of the dispersion is 1%;

[0123] 3. Add organic polysilazane and hydrophobic Al2O9Si3 inorganic nanoparticles to the second dispersion, wherein the mass ratios of organic polysilazane, lithium ion conductor nanoparticles LATP and hydrophobic Al2O9Si3 inorganic nanoparticles are (1:8:1, 1:7:2, 2:7:1), respectively, and magnetically stir the dispersion at room temperature to obtain 3 uniform dispersions. Centrifuge each of the prepared dispersions, wash the resulting precipitate with anhydrous ethanol, and vacuum dry the washed precipitate at 80°C for 24 hours, thereby obtaining 3 super hydrophobic materials that can conduct lithium ions in different proportions;

[0124] 4. Dispersing different proportions of super-hydrophobic materials capable of conducting lithium ions in ultra-dry xylene, respectively, and preparing three third dispersions by magnetic stirring at room temperature and subsequent ultrasonic dispersion;

[0125] 5. Use a spray gun to evenly spray the third dispersion on both sides of a 100 μm sulfide electrolyte membrane to prepare a coating, thereby obtaining a sulfide electrolyte membrane treated by spraying;

[0126] 6. The sulfide electrolyte membrane was placed in a vacuum drying oven at 80° C. for 8 hours to volatilize the xylene solvent, thereby obtaining three sulfide electrolyte membranes coated with super-hydrophobic materials capable of conducting lithium ions in different proportions.

[0127] Table 3 Electrolyte conductivity test results

[0128]

[0129] It can be seen from the above data that in Example 3, compared with the untreated sulfide electrolyte membrane, the static contact angle of water of the sulfide electrolyte membrane coated with the superhydrophobic material that can conduct lithium ions is significantly increased, and it still has a certain ionic conductivity.

[0130] According to the results in Tables 1-3, the coating constructed by the LATP nanoparticles coated with organic polysilazane and hydrophobic inorganic nanomaterials shows an increased contact angle with water compared to the untreated sulfide electrolyte membrane, thus having super-hydrophobic properties. The coating can transmit lithium ions, but it increases the resistance of the sulfide electrolyte membrane to a certain extent and has a certain hindering effect on the conduction of lithium ions. The hydrophobic properties and lithium ion conductivity are balanced, taking into account the air stability protection and ion conduction functions of the sulfide electrolyte membrane.

[0131] The super-hydrophobic material capable of conducting lithium ions provided by the embodiment of the present invention, wherein the ion conductor nanoparticles have good ion conduction performance. The organic polysilazane and hydrophobic nanoparticles are coated with super-hydrophobic properties, and based on their film-forming properties, they effectively isolate water molecules. On the basis of transferring lithium ions, the material can reduce the possibility of contact between the attached substrate and water, so that the substrate attached with the above-mentioned super-hydrophobic inorganic nanomaterial capable of conducting lithium ions has good stability in the air and can be stored in the air more conveniently.

[0132] The specific implementation methods described above have detailed descriptions of the objectives, technical solutions and beneficial effects of the present invention. The above descriptions are only specific implementation methods of the present invention, and the content is not limited to the above-mentioned embodiments. Any modifications and improvements made based on the present invention are within the protection scope of the present invention.

Claims

1. A super hydrophobic material capable of conducting lithium ions, comprising organic polysilazane, hydrophobic inorganic nanoparticles and lithium ion conductor nanoparticles.

2. The super-hydrophobic material capable of conducting lithium ions according to claim 1, characterized in that: The lithium ion conductor material is a polymer solid electrolyte, an inorganic solid electrolyte or a composite solid electrolyte, preferably a NASICON type oxide solid electrolyte containing lithium elements.

3. The super-hydrophobic material capable of conducting lithium ions according to claim 1, characterized in that: The super hydrophobic material capable of conducting lithium ions has a root mean square roughness greater than 30 nm and a surface energy less than 30 mJ / m 2 .

4. The super-hydrophobic material capable of conducting lithium ions according to claim 1, characterized in that: The super hydrophobic material capable of conducting lithium ions has a static contact angle greater than 130° and a rolling angle less than 10°.

5. A method for preparing a super-hydrophobic material capable of conducting lithium ions, characterized in that: The method comprises: providing hydrophobic inorganic nanoparticles, lithium ion conductor nanoparticles and organic polysilazane; The hydrophobic inorganic nanoparticles, lithium ion conductor nanoparticles and organic polysilazane are mixed and dried.

6. The method for preparing a super-hydrophobic material capable of conducting lithium ions according to claim 5, characterized in that: When preparing the hydrophobic inorganic nanomaterial, it includes the following steps: Providing inorganic nanoparticles; Dispersing the inorganic nanoparticles in a first dispersant to form a first dispersion containing the inorganic nanoparticles; The fluorine-containing silane coupling agent and silicate are added to the first dispersion, mixed and dried to form hydrophobic inorganic nanoparticles.

7. The method for preparing a super-hydrophobic material capable of conducting lithium ions according to claim 6, characterized in that: The mass ratio of the fluorine-containing silane coupling agent, the inorganic nanoparticles and the silicate is 0.1-2:1-5:1-5.

8. The method for preparing a super-hydrophobic material capable of conducting lithium ions according to claim 6, characterized in that: The first dispersant is an alcohol reagent.

9. The method for preparing a super-hydrophobic material capable of conducting lithium ions according to claim 6, characterized in that: The fluorine-containing silane coupling agent is one or more of tridecafluorooctyltrimethoxysilane, nonafluorohexyltrimethylsilane, and pentafluorophenyltriethylsilane; the silicate is one or more of methyl orthosilicate, ethyl orthosilicate, and isopropyl orthosilicate.

10. The method for preparing a super-hydrophobic material capable of conducting lithium ions according to claim 5, characterized in that: The lithium ion conductor material is a polymer solid electrolyte, an inorganic solid electrolyte or a composite solid electrolyte, preferably a NASICON type oxide solid electrolyte containing lithium elements.

11. The method for preparing a super-hydrophobic material capable of conducting lithium ions according to claim 5, wherein during the step of mixing and drying the hydrophobic inorganic nanoparticles, the lithium ion conductor nanoparticles and the organic polysilazane, the method comprises: Adding lithium ion conductor nanoparticles into a second dispersant for dispersion to form a second dispersion containing lithium ion conductor nanoparticles; The hydrophobic inorganic nanoparticles and the organic polysilazane are added into the second dispersion, mixed and dried.

12. The method for preparing a super-hydrophobic material capable of conducting lithium ions according to claim 11, characterized in that: The mass ratio of the organic polysilazane, the lithium ion conductor nanoparticles and the hydrophobic inorganic nanoparticles is 1-2:6-8:1-2.

13. A method for applying a super-hydrophobic material capable of conducting lithium ions, characterized in that: The steps include: Providing a super-hydrophobic material capable of conducting lithium ions, and adding the super-hydrophobic material to a third dispersant to form a third dispersion; The third dispersion is applied to the surface of the substrate and dried.

14. The application method of the super-hydrophobic material capable of conducting lithium ions according to claim 13, characterized in that: The third dispersant may be at least one of solvents such as xylene, tetrahydrofuran, heptane, and isopropanol.

15. The application method of the super-hydrophobic material capable of conducting lithium ions according to claim 13, characterized in that: The matrix is ​​a sulfide solid electrolyte.

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