CN112072050A - Inorganic ceramic modified slurry, preparation method, inorganic ceramic modified diaphragm and application - Google Patents
Inorganic ceramic modified slurry, preparation method, inorganic ceramic modified diaphragm and application Download PDFInfo
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Abstract
The invention discloses inorganic ceramic modified slurry and a preparation method thereof, and an inorganic ceramic modified diaphragm and application thereof.
Description
Technical Field
The invention belongs to the technical field of lithium ion batteries, and particularly relates to inorganic ceramic modified slurry and a preparation method thereof, and also relates to an inorganic ceramic modified diaphragm prepared from the inorganic ceramic modified slurry, and application of the inorganic ceramic modified diaphragm in preparation of a lithium ion battery.
Background
The diaphragm is used as one of four key materials of the lithium ion battery, can not only isolate the direct contact of the positive electrode and the negative electrode of the battery to avoid internal short circuit, but also provide a micropore channel for the exchange of lithium ions between the positive electrode and the negative electrode, and the performance of the diaphragm determines the characteristics of the lithium ion battery such as interface structure, internal resistance, discharge capacity, cycle service life, safety performance and the like.
At present, most of commercial lithium ion battery separators are made of polyolefin materials, but with the technological progress, people have higher and higher requirements on high-power and portable electronic equipment, especially the requirements on high current, high-rate discharge, higher heat resistance, good electrolyte adsorption and electrolyte retention capacity and the like, and polyolefin separators cannot meet the requirements, especially the application range is limited by poor electrolyte wettability and high heat shrinkage.
At present, the surface of a base film is mainly improved by coating an organic or inorganic coating (such as aluminum oxide and the like), but the problem of high water absorption rate exists when a water-based binder is adopted in the coating, the storage of a battery diaphragm is not facilitated, and the subsequent treatment cost is increased.
Disclosure of Invention
In view of the above, the present invention needs to provide an inorganic ceramic modified slurry and a preparation method thereof, in which oxidized β -cyclodextrin is used as a binder, so as to reduce the water absorption of a separator, and titanium dioxide core-shell particles are added to improve the rate and cycle performance of a lithium ion battery, so as to solve the above problems.
In order to achieve the purpose, the invention adopts the following technical scheme:
the invention provides inorganic ceramic modified slurry which is prepared from inorganic ceramic particle dispersion liquid, a surfactant, a binder, titanium dioxide core-shell particles and graphene oxide, wherein the binder is beta-cyclodextrin oxide.
Further, the preparation of the inorganic ceramic particle dispersion liquid comprises the following steps: mixing 4-7 parts of inorganic ceramic particles, 5-8 parts of magnesium hydroxide, 6-9 parts of silicon dioxide and 100-200 parts of deionized water according to the mass parts, adjusting the pH to 9-11, adding 1-2 parts of a dispersing agent, uniformly stirring, and carrying out high-speed shearing, stirring and dispersing for 30-60min to obtain an inorganic ceramic particle dispersion liquid.
Preferably, the inorganic ceramic particles are selected from boehmite.
Further, the preparation of the oxidized beta-cyclodextrin comprises the following steps: according to the mass parts, a mixed solution consisting of 3-5 parts of beta-cyclodextrin and 4-7 parts of hydrogen peroxide is sealed and insulated at 80-85 ℃ for 20-24h, then is dried by air blowing at 80-85 ℃ for 20-24h, and is dried in vacuum at 95-100 ℃ for 24-25h, so that the oxidized beta-cyclodextrin is obtained.
Further, the preparation of the titanium dioxide core-shell particles comprises the following steps:
mixing 6-10 parts of methyl methacrylate and 0.3-0.5 part of titanium dioxide according to the mass parts, and stirring and dispersing at a high speed for 10-20min to obtain a first solution;
dissolving 0.3-1.5 parts by mass of polyvinyl alcohol in 200 parts by mass of water at the temperature of 30-35 ℃, adding 0.06-0.1 part of hexadecane and 0.06-0.1 part of potassium persulfate, and uniformly mixing to obtain a second solution;
slowly dripping the first solution into the second solution, stirring for 3-4h to obtain a mixed solution, heating the mixed solution to 60-65 ℃, preserving heat for 10-12h, centrifuging, and drying to obtain the titanium dioxide core-shell particles.
The invention also provides a preparation method of the inorganic ceramic modified slurry, which comprises the steps of dissolving 3-5 parts of beta-cyclodextrin oxide in deionized water according to the mass ratio of 1:100, and adding inorganic ceramic particle dispersion liquid, 0.3-0.5 part of surfactant and titanium dioxide core-shell particles into the deionized water to obtain solution A;
adding 2-4 parts of graphene oxide into 20 parts of dimethylformamide according to the mass parts, and performing ultrasonic dispersion for 30-40min to obtain a solution B;
and adding the solution B into the solution A, and stirring for 10-12h to prepare inorganic ceramic modified slurry with the solid content of 30-40%.
The present invention further provides an inorganic ceramic modified separator comprising a base film and an inorganic ceramic coating layer prepared by applying the inorganic ceramic modified slurry according to any one of claims 1 to 5 to the surface of the base film.
Further, the base film is selected from polyolefin microporous films.
Further, the preparation of the inorganic ceramic modified diaphragm comprises the following steps:
coating the inorganic ceramic modified slurry on the surface of the base film by adopting a blade coating method, controlling the coating humidity and thickness, drying for 10-12h at 60-65 ℃ by blowing, and then drying for 20-24h at 60-65 ℃ in vacuum to obtain the inorganic ceramic modified diaphragm with the total thickness of 20-30 mu m, wherein the coating speed is 3-15m/min, and the roller speed ratio is 100-120%.
The invention also provides application of the inorganic ceramic modified diaphragm in preparation of a lithium ion battery.
Compared with the prior art, the invention has the following beneficial effects:
according to the invention, oxidized beta-cyclodextrin is used as a binder and added into the inorganic ceramic modified slurry, so that the moisture content of the diaphragm is reduced, the ionic conductivity of the diaphragm is improved, and the rate capability and the cycle performance of the lithium ion battery are improved.
In addition, titanium dioxide core-shell particles are added into the inorganic ceramic modified slurry, so that the moisture content, the thermal shrinkage rate and the rate capability of the diaphragm are improved, the discharge specific capacity and the cycle performance of a half battery assembled by the diaphragm are improved, and the electrochemical performance of the diaphragm is good.
The graphene oxide is added into the inorganic ceramic modified slurry, so that the electrochemical performance of the diaphragm is improved, specifically, the ionic conductivity of the diaphragm is improved, the electrochemical performance of the battery assembled by the diaphragm is further improved, and the liquid absorption rate and the porosity of the diaphragm are increased.
Detailed Description
In order that the invention may be more fully understood, reference will now be made to the specific embodiments illustrated. 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 invention discloses inorganic ceramic modified slurry, which is prepared from inorganic ceramic particle dispersion liquid, a surfactant, a binder, titanium dioxide core-shell particles and graphene oxide, wherein the binder is beta-cyclodextrin oxide.
According to the invention, the inorganic ceramic modified slurry is added with the beta-cyclodextrin oxide as a binder, and simultaneously the titanium dioxide core-shell particles and the graphene oxide, so that the electrochemical performance of the inorganic ceramic modified diaphragm obtained by coating is improved, specifically, the beta-cyclodextrin oxide coating film is a non-hydrophilic substance with a water contact angle of 37.9 degrees, so that the water absorption of the diaphragm is reduced, the titanium dioxide core-shell particles can improve the energy level structure of the titanium dioxide due to the unique core-shell structure, so that the electronic transmission and regeneration speed is improved, and the titanium dioxide core-shell particles are added into the slurry so as to improve the multiplying power and the cycle performance of the lithium ion battery. In addition, it should be noted that the surfactant in the slurry is mainly used for improving the dispersibility of each component in the slurry, and may be selected from surfactants conventionally used in the art, and in some specific embodiments of the present invention, the surfactant is selected from BYK-380.
Further, the preparation of the inorganic ceramic particle dispersion liquid comprises the following steps: mixing 4-7 parts of inorganic ceramic particles, 5-8 parts of magnesium hydroxide, 6-9 parts of silicon dioxide and 100-200 parts of deionized water according to the mass parts, adjusting the pH to 9-11, adding 1-2 parts of dispersing agent, uniformly stirring, shearing at high speed, stirring and dispersing for 30-60min, and filtering to obtain inorganic ceramic particle dispersion liquid. The inorganic ceramic particles are selected from boehmite.
It is understood that, in the inorganic ceramic particle dispersion, magnesium hydroxide is added to improve the oxygen index of the separator by virtue of its flame retardant property, and the basicity of magnesium hydroxide can reduce the damage of hydrofluoric acid to the battery, and the thermal conductivity of magnesium hydroxide can improve the thermal conductivity problem of the separator. While the inorganic ceramic particles may be selected from inorganic ceramic particles conventional in the art, in some embodiments of the present invention, boehmite is preferred, which also has flame retardant properties to further increase the oxygen index of the separator and thermal conductivity to further improve the thermal conductivity of the separator. Meanwhile, the boehmite and the magnesium hydroxide have small specific gravity and low hardness, and can improve the battery capacity, reduce the equipment loss and reduce the process cost. In addition, the dispersant added to the inorganic ceramic particle dispersion liquid is not particularly limited, and may be one conventionally used in the art, and preferably, in some embodiments of the present invention, the dispersant is selected from DN-582. The high-speed shear stirring is performed for the purpose of obtaining a uniform inorganic ceramic particle dispersion, and is preferably performed at 3000rpm, as long as the uniform dispersion can be achieved.
Further, the preparation of the oxidized beta-cyclodextrin comprises the following steps: according to the mass parts, a mixed solution consisting of 3-5 parts of beta-cyclodextrin and 4-7 parts of hydrogen peroxide is sealed and insulated at 80-85 ℃ for 20-24h, then is dried by air blowing at 80-85 ℃ for 20-24h, and is dried in vacuum at 95-100 ℃ for 24-25h, so that the oxidized beta-cyclodextrin is obtained. After the separator is coated with the slurry containing oxidized beta-cyclodextrin, because the contact angle of the oxidized beta-cyclodextrin coating film to water is 37.9 degrees, the contact angle is reduced by 68.4 percent compared with that of a pure PE microporous separator, the separator has lower hydrophilicity, and the water content of the coating film can be reduced.
Further, the preparation of the titanium dioxide core-shell particles comprises the following steps:
mixing 6-10 parts of methyl methacrylate and 0.3-0.5 part of titanium dioxide according to the mass part, and then stirring and dispersing at a high speed for 10-20min to obtain a first solution, wherein the purpose of stirring at a high speed is to realize uniform dispersion, is not particularly limited, and preferably, the rotating speed is 3000 rpm;
dissolving 0.3-1.5 parts by mass of polyvinyl alcohol in 200 parts by mass of water at the temperature of 30-35 ℃, adding 0.06-0.1 part of hexadecane and 0.06-0.1 part of potassium persulfate, and uniformly mixing to obtain a second solution;
slowly dripping the first solution into the second solution, stirring for 3-4h to obtain a mixed solution, heating the mixed solution to 60-65 ℃, preserving heat for 10-12h, centrifuging, and drying to obtain the titanium dioxide core-shell particles.
The titanium dioxide core-shell particles with the core-shell being titanium dioxide are prepared by the preparation method, the energy level structure of the titanium dioxide can be improved, the electronic transmission and regeneration speed can be increased, and the multiplying power and the cycle performance of the lithium ion battery can be improved by adding the titanium dioxide core-shell particles into the slurry. It should be noted that, the centrifugation and drying are all conventional means in the art, and the purpose of the centrifugation and drying is to separate and dry the titanium dioxide core-shell particles, which is not particularly limited, and in some specific embodiments of the present invention, the centrifuged product is dried at 80 ℃ for 12 hours.
Further, dissolving 3-5 parts of oxidized beta-cyclodextrin in deionized water according to the mass ratio of 1:100, and adding inorganic ceramic particle dispersion liquid, 0.3-0.5 part of surfactant and titanium dioxide core-shell particles to obtain solution A;
adding 2-4 parts of graphene oxide by mass into dimethylformamide for ultrasonic dispersion for 30-40min to obtain a solution B;
and adding the solution B into the solution A, and stirring for 10-12h to prepare inorganic ceramic modified slurry with the solid content of 30-40%.
In a second aspect of the present invention, there is disclosed an inorganic ceramic modified membrane, which comprises a base membrane and an inorganic ceramic coating layer, wherein the inorganic ceramic coating layer is prepared by coating the inorganic ceramic modified slurry according to the first aspect of the present invention on the surface of the base membrane.
Further, the base film in the present invention may be selected from base films for lithium ion batteries, which are conventional in the art, and the thickness of the base film, etc. are not particularly limited and may be selected according to the need of assembling the battery as needed, and in some specific embodiments of the present invention, the base film is selected from polyolefin microporous films.
Further, the preparation of the inorganic ceramic modified diaphragm comprises the following steps:
coating the inorganic ceramic modified slurry on the surface of the base film by adopting a blade coating method, controlling the coating humidity and thickness, drying for 10-12h at 60-65 ℃ by blowing, and then drying for 20-24h at 60-65 ℃ in vacuum to obtain the inorganic ceramic modified diaphragm with the total thickness of 20-30 mu m, wherein the coating speed is 3-15m/min, and the roller speed ratio is 100-120%.
The third aspect of the present invention discloses an application of the inorganic ceramic modified membrane according to the second aspect of the present invention in the preparation of a lithium ion battery, where the lithium ion battery may be any type of battery in the art, and includes a positive electrode, a negative electrode, a membrane and an electrolyte, the selection of the positive electrode, the negative electrode and the electrolyte is not particularly limited, and the assembly manner of the lithium ion battery may also adopt a conventional assembly method in the art, and therefore, details thereof are not repeated here.
The technical solution of the present invention will be more clearly described below with reference to specific examples.
Example 1
The preparation of the inorganic ceramic modified slurry in this embodiment specifically comprises the following steps:
preparing titanium dioxide core-shell particles: mixing 6 parts of methyl methacrylate and 0.3 part of titanium dioxide according to the mass part, and stirring and dispersing at a high speed of 3000r/min for 10min to obtain a first solution; dissolving 0.3 part of polyvinyl alcohol in 120 parts of water with the water temperature of 30-35 ℃, adding 0.06 part of hexadecane and 0.06 part of potassium persulfate, and uniformly mixing to obtain a second solution; slowly dripping the first solution into the second solution, stirring for 3h after dripping, heating to 60-65 ℃, preserving heat for 10h, centrifuging, and washing with water for 3 times.
Preparing inorganic ceramic particle dispersion liquid: mixing 4 parts of boehmite, 5 parts of magnesium hydroxide, 6 parts of silicon dioxide and 100 parts of deionized water according to the parts by mass, adjusting the pH to 9-11, adding 1 part of dispersing agent DN-582, uniformly stirring, shearing, stirring and dispersing at a high speed of 3000r/min for 30min, and filtering to obtain the inorganic ceramic particle dispersion liquid.
Preparing oxidized beta-cyclodextrin: mixing 3 parts of beta-cyclodextrin and 4 parts of hydrogen peroxide according to the mass parts, sealing and insulating for 20h at 80-85 ℃, then blowing and drying for 20h at 80-85 ℃, and then vacuum drying for 24h at 95-100 ℃ to obtain the oxidized beta-cyclodextrin.
Preparing inorganic ceramic modified slurry: dissolving 3 parts of binder oxidized beta-cyclodextrin in deionized water according to the mass ratio of 1:100, and adding inorganic ceramic particle dispersion liquid, 0.3 part of surfactant BYK-380 and the prepared titanium dioxide core-shell particles to obtain mixed liquid; and ultrasonically dispersing 2 parts of graphene oxide in dimethylformamide for 30min, adding the graphene oxide into the mixed solution, and magnetically stirring for 10h to obtain coating slurry with the solid content of 30%.
Preparing an inorganic ceramic modified diaphragm:
coating the inorganic ceramic modified slurry on the surface of a 14-micron-sized polypropylene microporous diaphragm by adopting a blade coating method at a coating speed of 3m/min and a roll speed ratio of 100%, controlling the single-side coating wet thickness, carrying out forced air drying at 60-65 ℃ for 10h, and then carrying out vacuum drying at 60-65 ℃ for 20h to obtain the inorganic ceramic modified diaphragm with the total thickness of 20 microns.
Example 2
The preparation of the inorganic ceramic modified slurry in this embodiment specifically comprises the following steps:
preparing titanium dioxide core-shell particles: mixing 10 parts of methyl methacrylate and 0.5 part of titanium dioxide according to the mass part, and stirring and dispersing at a high speed of 3000r/min for 10min to obtain a first solution; dissolving 1.5 parts of polyvinyl alcohol in 200 parts of water with the water temperature of 30-35 ℃, adding 0.1 part of hexadecane and 0.1 part of potassium persulfate, and uniformly mixing to obtain a second solution; slowly dripping the first solution into the second solution, stirring for 4h after dripping, heating to 60-65 ℃, keeping the temperature for 12h, centrifuging, and washing with water for 5 times.
Preparing inorganic ceramic particle dispersion liquid: mixing 7 parts of boehmite, 8 parts of magnesium hydroxide, 9 parts of silicon dioxide and 200 parts of deionized water according to parts by mass, adjusting the pH to 9-11, adding 2 parts of a dispersing agent DN-582, uniformly stirring, shearing, stirring and dispersing at a high speed of 3000r/min for 60min, and filtering to obtain the inorganic ceramic particle dispersion liquid.
Preparing oxidized beta-cyclodextrin: mixing 5 parts of beta-cyclodextrin and 7 parts of hydrogen peroxide according to the mass parts, sealing and insulating for 24 hours at 80-85 ℃, then blowing and drying for 24 hours at 80-85 ℃, and then vacuum drying for 25 hours at 95-100 ℃ to obtain the oxidized beta-cyclodextrin.
Preparing inorganic ceramic modified slurry: dissolving 5 parts of binder oxidized beta-cyclodextrin in deionized water according to the mass ratio of 1:100, and adding inorganic ceramic particle dispersion liquid, 0.5 part of surfactant BYK-380 and the prepared titanium dioxide core-shell particles to obtain mixed liquid; and ultrasonically dispersing 4 parts of graphene oxide in dimethylformamide for 40min, adding the graphene oxide into the mixed solution, and magnetically stirring for 12h to obtain coating slurry with the solid content of 40%.
Preparing an inorganic ceramic modified diaphragm:
and (3) coating one side of the inorganic ceramic modified slurry on the surface of a 14-micron-thickness polypropylene microporous diaphragm by adopting a blade coating method at a coating speed of 15m/min and a roll speed ratio of 120%, controlling the coating humidity, carrying out forced air drying at 60-65 ℃ for 10 hours, and then carrying out vacuum drying at 60-65 ℃ for 20 hours to obtain the inorganic ceramic modified diaphragm with the total thickness of 30 microns.
Test example
The inorganic ceramic modified diaphragm prepared by the invention is subjected to related performance tests, and specifically comprises the following steps:
and (3) testing the liquid absorption rate: (1) intercepting a diaphragm sample;
(2) the septum sample volume was measured and recorded as V1;
(3) placing the container filled with the electrolyte on an electronic balance, enabling the reading to return to zero, fixing a ring by using a thin wire, and recording the reading of the balance as M1 after the ring is completely immersed and suspended in the electrolyte;
(4) fixing the diaphragm sample on the circular ring, repeating the step (3), and recording the reading of the balance as M2 after 1-180 minutes;
by the formula: the liquid absorption rate L was calculated by (ρ V1+ M1-M2)/V1, where ρ is the electrolyte density.
And (3) porosity measurement test: (1) folding the diaphragm into 6 stacks, flattening, pressing and removing air in the diaphragm;
(2) cutting the stacked diaphragm according to the cutting sample plate, measuring the cut sample to obtain the area S of the sample, measuring the thickness of the sample for 10 times or 20 times, and calculating the average value B;
(3) measuring the weight of the diaphragm by using an electronic balance, wherein the measuring times are 3 times to obtain an average value M;
the porosity p ═ 100% (density of the separator raw material S × B-M)/(density of the separator raw material S × B) ], was calculated by a formula.
And (3) ion conductivity test: soaking the diaphragm for more than 2h, drying with filter paper, clamping the diaphragm between two stainless steel sheets, sealing with a button shell, and performing AC impedance method with AC current of disturb mv amplitude and frequency of 1-100000 Hz.
The inorganic ceramic modified diaphragm of the invention has excellent organic solvent resistance and electronic insulation property through tests, wherein the liquid absorption rate of the inorganic ceramic modified diaphragm in the example 1 is 0.91g/cm3The porosity is 75 percent, and the ionic conductivity of the coating film is high and reaches 2.02 multiplied by 10-3S/cm; the specific capacity of 0.5C of the inorganic ceramic modified diaphragm assembled battery in the embodiment 1 reaches 2309mAh/g, the specific capacity of the battery after 0.5C is cycled for 1000 circles is stabilized at about 1000mAh/g, and the first coulombic efficiency is 79%.
Comparative example 1
In this comparative example, in which the titanium dioxide of example 1 was used and no core shell particle was prepared, the other components and preparation were the same as in example 1, the liquid absorption rate of the inorganic ceramic modified membrane was 0.84g/cm3Porosity of 73% and ionic conductivity of 1.72X 10-3S/cm; the first 0.5C discharge specific capacity of the battery assembled in the same way as in the embodiment 1 reaches 2289mAh/g, and the specific capacity of the battery after 0.5C circulation for 1000 circles is stabilized at about 995mAh/gRight, the first coulombic efficiency was 75%.
Comparative example 2
The comparative example, in which unoxidized beta-cyclodextrin was used and other components and preparation were the same as in example 1, had a liquid absorption rate of 0.78g/cm for the inorganic ceramic modified membrane3Porosity of 70% and ionic conductivity of 1.75X 10-3S/cm; the initial discharge specific capacity of 0.5C of the battery assembled in the same way as in the embodiment 1 reaches 2268mAh/g, the specific capacity of the battery after 0.5C circulation for 1000 circles is stabilized to be about 983mAh/g, and the initial coulombic efficiency is 76%.
Comparative example 3
In this comparative example, no beta-cyclodextrin oxide was added and the other components and preparation were the same as in example 1. In the comparative example, the inorganic ceramic modified separator had a liquid absorption rate of 186%, a porosity of 72%, and an ionic conductivity of 1.76X 10-3S/cm; the first 0.5C discharge specific capacity of the battery assembled in the same way as in the embodiment 1 reaches 2283mAh/g, the specific capacity of the battery after 1000 cycles of 0.5C circulation is stabilized at about 973mAh/g, and the first coulombic efficiency is 72%.
Comparative example 4
In this comparative example, no graphene oxide was added, and the other components and preparation were the same as in example 1. The liquid absorption rate of the inorganic ceramic modified diaphragm in the comparative example is 0.82g/cm3Porosity of 71% and ionic conductivity of 1.88X 10-3S/cm; the specific capacity of 0.5C initial discharge of the battery assembled in the same way as in the embodiment 1 reaches 2277mAh/g, the specific capacity of the battery after 0.5C circulation for 1000 circles is stabilized to be about 984mAh/g, and the initial coulombic efficiency is 73%.
The technical features of the embodiments described above may be arbitrarily combined, and for the sake of brevity, all possible combinations of the technical features in the embodiments described above are not described, but should be considered as being within the scope of the present specification as long as there is no contradiction between the combinations of the technical features.
The above-mentioned embodiments only express several embodiments of the present invention, and the description thereof is more specific and detailed, but not construed as limiting the scope of the invention. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the inventive concept, which falls within the scope of the present invention. Therefore, the protection scope of the present patent shall be subject to the appended claims.
Claims (10)
1. The inorganic ceramic modified slurry is characterized by being prepared from inorganic ceramic particle dispersion liquid, a surfactant, a binder, titanium dioxide core-shell particles and graphene oxide, wherein the binder is beta-cyclodextrin oxide.
2. The inorganic ceramic modification slurry of claim 1, wherein the preparation of the inorganic ceramic particle dispersion comprises the steps of: mixing 4-7 parts of inorganic ceramic particles, 5-8 parts of magnesium hydroxide, 6-9 parts of silicon dioxide and 100-200 parts of deionized water according to the mass parts, adjusting the pH to 9-11, adding 1-2 parts of a dispersing agent, uniformly stirring, and carrying out high-speed shearing, stirring and dispersing for 30-60min to obtain an inorganic ceramic particle dispersion liquid.
3. The inorganic ceramic modification slurry of claim 2, wherein the inorganic ceramic particles are selected from boehmite.
4. The inorganic ceramic modifying slurry of claim 1, wherein said oxidized β -cyclodextrin is prepared by the steps of: according to the mass parts, a mixed solution consisting of 3-5 parts of beta-cyclodextrin and 4-7 parts of hydrogen peroxide is sealed and insulated at 80-85 ℃ for 20-24h, then is dried by air blowing at 80-85 ℃ for 20-24h, and is dried in vacuum at 95-100 ℃ for 24-25h, so that the oxidized beta-cyclodextrin is obtained.
5. The inorganic ceramic modified slurry of claim 1, wherein the preparation of the titanium dioxide core-shell particles comprises the steps of:
mixing 6-10 parts of methyl methacrylate and 0.3-0.5 part of titanium dioxide according to the mass parts, and stirring and dispersing at a high speed for 10-20min to obtain a first solution;
dissolving 0.3-1.5 parts by mass of polyvinyl alcohol in 200 parts by mass of water at the temperature of 30-35 ℃, adding 0.06-0.1 part of hexadecane and 0.06-0.1 part of potassium persulfate, and uniformly mixing to obtain a second solution;
slowly dripping the first solution into the second solution, stirring for 3-4h to obtain a mixed solution, heating the mixed solution to 60-65 ℃, preserving heat for 10-12h, centrifuging, and drying to obtain the titanium dioxide core-shell particles.
6. The method for preparing the inorganic ceramic modified slurry according to any one of claims 1 to 5, wherein 3 to 5 parts by mass of beta-cyclodextrin oxide is dissolved in deionized water in a mass ratio of 1:100, and an inorganic ceramic particle dispersion, 0.3 to 0.5 part of a surfactant and core-shell particles of titanium dioxide are added thereto to obtain a solution A;
adding 2-4 parts of graphene oxide into 20 parts of dimethylformamide according to the mass parts, and performing ultrasonic dispersion for 30-40min to obtain a solution B;
and adding the solution B into the solution A, and stirring for 10-12h to prepare inorganic ceramic modified slurry with the solid content of 30-40%.
7. An inorganic ceramic modified membrane, which comprises a base membrane and an inorganic ceramic coating, wherein the inorganic ceramic coating is prepared by coating the inorganic ceramic modified slurry of any one of claims 1 to 5 on the surface of the base membrane.
8. The inorganic ceramic modified separator according to claim 7, wherein said base film is selected from polyolefin microporous films.
9. The inorganic ceramic modified membrane of claim 7, wherein the preparation of the inorganic ceramic modified membrane comprises the steps of:
coating the inorganic ceramic modified slurry on the surface of the base film by adopting a blade coating method, controlling the coating humidity and thickness, drying for 10-12h at 60-65 ℃ by blowing, and then drying for 20-24h at 60-65 ℃ in vacuum to obtain the inorganic ceramic modified diaphragm with the total thickness of 20-30 mu m, wherein the coating speed is 3-15m/min, and the roller speed ratio is 100-120%.
10. Use of the inorganic ceramic modified separator of claim 7 for the preparation of a lithium ion battery.
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