CN111200093B - Ceramic particle and preparation method and application thereof - Google Patents
Ceramic particle and preparation method and application thereof Download PDFInfo
- Publication number
- CN111200093B CN111200093B CN202010025870.XA CN202010025870A CN111200093B CN 111200093 B CN111200093 B CN 111200093B CN 202010025870 A CN202010025870 A CN 202010025870A CN 111200093 B CN111200093 B CN 111200093B
- Authority
- CN
- China
- Prior art keywords
- ceramic
- ceramic particles
- methyl methacrylate
- deionized water
- particles
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Images
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/403—Manufacturing processes of separators, membranes or diaphragms
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/409—Separators, membranes or diaphragms characterised by the material
- H01M50/411—Organic material
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/409—Separators, membranes or diaphragms characterised by the material
- H01M50/44—Fibrous material
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The application discloses a ceramic particle and a preparation method and application thereof. The ceramic particles of the present application have a methyl methacrylate modification on the surface thereof. The ceramic particles are modified by methyl methacrylate on the surface, so that the ceramic particles can have better liquid absorption rate and liquid retention capacity when used as a ceramic coating of a battery diaphragm, and the air permeability and the heat resistance of the battery diaphragm are improved, so that the cycle performance and the speed capacity of a lithium battery are improved.
Description
Technical Field
The application relates to the field of battery diaphragm materials, in particular to ceramic particles and a preparation method and application thereof.
Background
The diaphragm is used as one of four core components of the lithium ion battery, and influences the battery capacity, internal resistance, current density, cycle performance and safety performance. With the development of lithium batteries, the requirements on the performance of the diaphragm, particularly the safety performance, are higher and higher, and the diaphragm coating technology becomes an effective way for greatly improving the safety performance of the diaphragm. The ceramic coating provides a framework for the flexible diaphragm, improves the wear-resisting property of the diaphragm, prevents the penetration of lithium dendrites, reduces thermal shrinkage, improves the temperature resistance, stabilizes the pore along with the temperature change, and can effectively improve the safety performance of the battery. In particular, the appearance of ceramic coatings for the existing wet-process PE films directly reverses the disadvantages of the wet-process PE films, so that the ceramic-coated PE films have been developed into the mainstream of the market today.
The mainstream product of the ceramic coating is high-performance alpha-alumina micropowder, but the application of alumina reaches a bottleneck through the development of the years, and no further development or application is available in the late stage. For the development of alumina, a new research or application direction has not been proposed yet. Furthermore, although the properties of alpha-alumina coatings have been able to meet most requirements; however, for some high-end battery products, the development speed thereof has far missed the use requirements of the applications.
Disclosure of Invention
The object of the present application is to provide a new ceramic particle, a method for its preparation and its use.
In order to achieve the purpose, the following technical scheme is adopted in the application:
one aspect of the present application discloses a ceramic particle having a methyl methacrylate modified modification on a surface thereof.
The ceramic particles are modified by methyl methacrylate on the surface, so that the ceramic particles can have better liquid absorption rate and liquid retention capacity when being used as a ceramic coating of a battery diaphragm, and the air permeability and the heat resistance of the battery diaphragm are improved to different degrees, so that the cycle performance and the rate capacity of a lithium battery are improved. It can be understood that the key point of the application is that the surface of the ceramic particle is modified by methyl methacrylate; as for the specific ceramic particles, ceramic materials used in existing ceramic-coated separators may be used, and are not particularly limited herein.
Preferably, the ceramic particles are ceramic micro/nanospheres prepared from at least one of silicon dioxide, aluminum oxide, aluminum nitride, titanium dioxide, vanadium pentoxide and barium titanate.
Another aspect of the present application discloses a method for preparing the ceramic particles of the present application, comprising the steps of,
(1) dispersing ceramic particles into absolute ethyl alcohol, then sequentially adding deionized water, ammonia water and a modifier, and uniformly stirring to obtain a mixture; performing ultrasonic stirring on the mixture, namely performing stirring at the speed of 100-120r/min for 36-60h while performing ultrasonic stirring, wherein the ultrasonic stirring conditions are as follows: ultrasonic treatment for 1s-1.5s, interval for 2s-2.5s, and frequency for 1.3-1.78 khz; after ultrasonic stirring is finished, centrifugally collecting ceramic particles, washing the ceramic particles with deionized water at least once, and then drying the ceramic particles in vacuum at 50-80 ℃ to obtain modifier-modified ceramic particles;
(2) dispersing the ceramic particles modified by the modifier prepared in the step (1) in deionized water to prepare suspension; adding methyl methacrylate and potassium persulfate into deionized water to prepare a methyl methacrylate solution; adding methyl methacrylate solution into the suspension, and carrying out reflux reaction for 5-8h under the protection of nitrogen; washing the obtained product with deionized water for at least three times, and then carrying out vacuum drying for 12-14h at the temperature of 60-80 ℃ to obtain ceramic particles with the surfaces modified and modified by methyl methacrylate;
in the step (1), the modifier is at least one of methacryloxypropyltrimethoxysilane, vinyltriethoxysilane, 3-methacryloxypropyltris (trimethylsiloxy) silane, and tetraisopropoxybis (dioctylphosphite-oxy) titanate.
Preferably, in the step (1), the weight ratio of the ceramic particles to the absolute ethyl alcohol is 1:15-1: 30.
Preferably, in the step (1), the weight ratio of the deionized water to the ceramic particles is 1:1-2: 1.
Preferably, in the step (1), the weight ratio of the added deionized water to the ammonia water is 1:1.5-1: 2.5.
Preferably, in the step (1), the weight ratio of the modifier to the ceramic particles is 1:5-3: 5.
It should be noted that, the step (1) is mainly to prepare ceramic particles modified by a modifier, so as to prepare ceramic particles modified and modified by methyl methacrylate in the following; in general, the weight ratio of the ceramic particles to the modifier to the absolute ethyl alcohol to the deionized water to the ammonia water is 1 (15-30) to 1-2 to 1.5 to 5 to 0.2-0.6; it will be appreciated that the above weight ratios are primarily intended to more effectively modify the surface of the ceramic particles, minimizing material waste.
Preferably, the weight ratio of the ceramic particles modified by the modifying agent to the deionized water in the suspension of the step (2) is 1:80-1: 120.
Preferably, in the step (2), the weight ratio of the methyl methacrylate to the potassium persulfate is 60:1-40: 1.
Preferably, in the methyl methacrylate solution in the step (2), the weight ratio of the methyl methacrylate to the deionized water is 1:100-20: 100.
It should be noted that the weight ratio of the ceramic particles modified by the modifying agent to the deionized water is mainly to ensure that the ceramic particles modified by the modifying agent can be effectively dispersed so as to facilitate the subsequent surface modification reaction; similarly, the weight ratio of methyl methacrylate to potassium persulfate and the weight ratio of methyl methacrylate to deionized water are also used for ensuring that the reaction components can be effectively dispersed for subsequent reaction; as regards the final ratio of methyl methacrylate to ceramic particles, this may be determined according to requirements, for example, in one implementation of the present application the ceramic particles are surface-modified with a weight ratio of 1:3 of ceramic particles to methyl methacrylate, i.e. with three times the weight of the ceramic particles of methyl methacrylate. It is understood that the higher the amount of methyl methacrylate used, the more complete the surface modification of the corresponding ceramic particles, and the smaller the number of unmodified ceramic particles; generally, the use requirement can be satisfied by adopting methyl methacrylate with three times of the weight of the ceramic particles, and the surface modification effect cannot be obviously enhanced by increasing the using amount of the methyl methacrylate.
In yet another aspect, the present application discloses the use of the ceramic particles of the present application in the preparation of a ceramic coating slurry or a ceramic coated separator.
Yet another aspect of the present application discloses a ceramic coating slurry employing the ceramic particles of the present application.
Yet another aspect of the present application discloses a ceramic coated membrane employing the ceramic particles of the present application, or the ceramic coating slurry of the present application.
One more aspect of the present application discloses a battery employing the ceramic coated separator of the present application.
Due to the adoption of the technical scheme, the beneficial effects of the application are as follows:
the ceramic particles are modified by methyl methacrylate on the surface, so that the ceramic particles can have better liquid absorption rate and liquid retention capacity when being used as a ceramic coating of a battery diaphragm, and the air permeability and the heat resistance of the battery diaphragm are improved, so that the cycle performance and the speed capacity of a lithium battery are improved.
Drawings
FIG. 1 is a scanning electron microscope image comparing a ceramic coated membrane of example 1 of the present application with a base membrane, wherein a is a scanning electron microscope image of the base membrane and b is a scanning electron microscope image of the coated surface of the ceramic coated membrane;
FIG. 2 is a liquid absorption test chart of the ceramic coated separator of example 1 of the present application and comparative test 1, wherein a is a test chart of comparative test 1, and b is a test chart of example 1;
fig. 3 is a contact angle test chart of the ceramic coated separator of example 1 of the present application and comparative test 1, a being a test chart of comparative test 1, b being a test chart of example 1.
Detailed Description
The existing ceramic coating diaphragm has no new research progress and direction in the aspect of ceramic particles, particularly in the aspect of research of alumina, and has already caused the bottleneck of ceramic coating. In order to break through the bottleneck, and simultaneously also in order to meet some high-end application requirements of the ceramic coating diaphragm, a novel modified ceramic particle is developed, the surface of the ceramic particle is improved, the overall performance of the ceramic coating is improved, the bottleneck of the development of the ceramic coating is broken, and a new direction is provided for the research and development of the ceramic coating.
Specifically, the ceramic particles of the present application are modified with methyl methacrylate on the surface thereof; when the modified ceramic particles are used as a ceramic coating, the ceramic coating has good thermal shrinkage performance of the ceramic coating; moreover, through methyl methacrylate modification, after the swelled polymethyl methacrylate microspheres are immersed in an electrolyte solution, a gel electrolyte is formed, so that the electrolyte is more stable; the porous structure of the coating is beneficial to the swelling of the electrolyte and the transportation of lithium ions; compared with a common ceramic coating, the ceramic coating diaphragm adopting the ceramic particles has the advantages that the liquid absorption rate, the air permeability increment, the heat resistance and the like are improved; the ceramic coating diaphragm assembled lithium battery prepared by the ceramic particles can improve the cycle performance and the speed capability of the lithium battery.
The present application is described in further detail below with reference to specific embodiments and the attached drawings. The following examples are intended to be illustrative of the present application only and should not be construed as limiting the present application.
Example 1
In this example, methyl methacrylate modification was performed on the surface of 0.4 μm alumina ceramic powder as D50, the ceramic particles after surface modification were made into slurry, which was coated on a 12 μm wet PE film base film to make a ceramic coating membrane, and the liquid absorption rate, liquid retention rate, air permeability, and thermal shrinkage of the ceramic coating membrane were tested.
The preparation method of the methyl methacrylate modified ceramic powder comprises the following steps:
(1) 100g of ceramic powder is taken and dispersed in 2.5L of absolute ethyl alcohol, and then 130 ml of deionized water, 68g of ammonia water and 60g of modifier methacryloxypropyl trimethoxysilane are sequentially added and stirred uniformly; then, carrying out ultrasonic treatment and stirring, wherein the process is carried out synchronously, the stirring speed is 120r/min, and the ultrasonic conditions are as follows: ultrasonic treatment is carried out for 1ss, the gap is 2.5s, the upper limit of the temperature is not set, the frequency is 1.5khz, and the actual stirring is carried out for 48 hours; the ceramic nanospheres modified by the modifying agent are obtained by centrifuging at the speed of 1000r/min for 2h and at the temperature of 25 ℃, then collecting the ceramic nanospheres modified by the modifying agent, thoroughly washing the ceramic nanospheres with deionized water, and finally drying the ceramic nanospheres at the temperature of 60 ℃ in vacuum;
(2) dispersing 10g of the prepared modifier modified ceramic nanospheres into 900mL of deionized water, and placing the mixture into a 2.5L nitrogen-protected three-neck flask; adding 30g of methyl methacrylate and 0.5g of potassium persulfate into 1L of deionized water, and then adding the mixture into a three-neck flask; after the mixture is refluxed for 6 hours, the obtained product is centrifugally washed for three times by deionized water, and residual monomers and initiators are removed; and (3) drying the final product at 60 ℃ in vacuum for 12h to obtain the ceramic nanosphere with the methyl methacrylate modified and modified surface.
The ceramic nanosphere modified and modified by methyl methacrylate prepared in the example is prepared into ceramic slurry for coating and preparing a coating diaphragm, and the details are as follows:
preparing ceramic slurry: 55g of deionized water, 0.5g of plasticizer, 35g of the methyl methacrylate modified ceramic nanosphere prepared in the example, 5g of binder and 2.1g of dispersant were mixed and stirred at a speed of 80r/mim for 2 hours to obtain the ceramic slurry of the example. Wherein, the plasticizer is sodium carboxymethylcellulose, the binder is polyacrylic resin, and the dispersant is polyether compound.
Coating with 4.2g/m micro-gravure roller 2 And coating the ceramic slurry on the surface of the base film on one side, and drying to obtain the ceramic coating diaphragm of the embodiment.
The base film and the ceramic-coated diaphragm of this example were observed by scanning electron microscopy, and the results are shown in fig. 1, in which a is a scanning electron microscopy of the base film, and b is a scanning electron microscopy of the coated surface of the ceramic-coated diaphragm. The results in FIG. 1 show that the ceramic coating prepared in this example has a uniform coating and a regular morphology.
Comparative experiment 1
The same alumina ceramic powder as in example 1 was used in this test, except that the alumina ceramic powder was directly used in this test to prepare a ceramic slurry without any modification of the surface. The ceramic slurry formulation of this test was the same as example 1 and the same base film and method as in example 1 was used to make the same specification ceramic coated separator. The test was carried out in the same manner as in example 1 except that the alumina ceramic powder was used directly for preparing the ceramic slurry.
The ceramic coating diaphragms of example 1 and comparative test 1 were subjected to a thickness test, a gas permeability test, an areal density test, a thermal shrinkage test, a contact angle test and a liquid absorption rate test, and the properties of the prepared ceramic coating diaphragms before and after the modification of the surface of the same alumina ceramic particle with methyl methacrylate were analyzed by comparison. The details are as follows:
and (3) thickness testing: the thickness of the ceramic coating diaphragm is tested by two methods respectively, wherein the first method comprises the following steps: the measurement is carried out by referring to GB/T6672-2001, a handheld thickness meter is adopted to measure the thickness, 5 points are taken to measure every 5cm along the TD direction of the film, and the average value of the measurement is the thickness of the film; the second method comprises the following steps: the measurement is carried out by referring to GB/T6672-2001, a Mark thickness gauge with a flat contact head is adopted for measurement, the gauge is calibrated and cleared before the measurement, the contact surface is kept clean, one point is taken for measurement every 5cm along the TD direction of the film, and the average value of 5 points is measured to be the thickness of the film.
And (3) testing the air permeability value: taking 5 samples and testing by using a ventilation instrument according to GB/T458-2008, and taking the average value of the measurement as the ventilation value of the sample to be measured, wherein the unit is s/100 mL.
And (3) testing the areal density: cutting 10 × 10cm diaphragm, weighing, and dividing the mass by the area to obtain the surface density in g/m 2 。
Thermal shrinkage test: the thermal shrinkage rate of the ceramic coating diaphragm at 150 ℃ for 1h is tested, and the test is carried out according to polyolefin diaphragm for lithium ion battery GB/T36363-2018.
Contact angle test: dropping the electrolyte on the surface of the diaphragm sample, testing the contact angle of the diaphragm and the electrolyte by adopting a video contact angle meter, and repeating for 5 times to obtain an average value; wherein the electrolyte is LiPF with the concentration of 1mol/L 6 The solvent composition of the solution is volume ratio of dimethyl carbonate DMC to ethylene carbonate EC to methyl ethyl carbonate EMC 1:1: 1.
Liquid absorption rate: the coating film of 10X 10cm in size was weighed to a mass of W 0 Immersing in the mixed solution of Ethylene Carbonate (EC) and Propylene Carbonate (PC) at room temperature at a ratio of 1:1, standing for 2h, sucking the electrolyte on the surface with filter paper, weighing, and recording the mass as W 1 Then continuously standing at room temperature for 10min, weighing again, and recording the mass as W 2 ；
Liquid absorption rate ═ W 2 -W 0 )/W 0
Retention rate of (W) 1 -W 2 )/(W 1 -W 0 )
The results of the tests are shown in Table 1.
TABLE 1 ceramic coating diaphragm Performance test results
The results in table 1 show that the liquid absorption rate and the liquid retention rate of the coating diaphragm prepared by using the alumina ceramic particles modified and modified by methyl methacrylate in the example 1 are significantly higher than those of the alumina ceramic coating without modification in the same specification; in addition, the air permeability of the alumina ceramic coating diaphragm modified and modified by methyl methacrylate is obviously superior to that of the alumina ceramic coating diaphragm without modification in the same specification; in the aspect of thermal shrinkage, the thermal shrinkage of the alumina ceramic coating diaphragm modified and modified by methyl methacrylate is obviously smaller.
A drop of electrolyte was applied to the surface of the ceramic-coated separators of example 1 and comparative test 1 to test the liquid absorption capacity and wetting capacity, and the test results are shown in fig. 2; in the figure, a is a test chart of comparative experiment 1, and b is a test chart of example 1. The results of fig. 2 show that the wettability and liquid-absorbing ability of the ceramic coating membrane prepared from the modified ceramic particles of example 1 are significantly better.
The graph of the contact angle test results of the ceramic coating separators of example 1 and comparative test 1 is shown in fig. 3; in the figure, a is a test chart of comparative experiment 1, and b is a test chart of example 1. The contact angle is the angle between the liquid drop edge tangent angle and the horizontal direction, and the larger the angle, the poorer the wettability with the electrolyte, and the smaller the angle, the better the affinity. The results of fig. 3 show that the affinity and wettability of the ceramic coated membrane prepared from the modified ceramic particles of example 1 are significantly better than those of the ceramic coated membrane of comparative test 1.
Example 2
In this example, silica particles, aluminum nitride particles, titanium dioxide particles, vanadium pentoxide particles, and barium titanate particles of the same specification were used in place of the alumina particles of example 1, respectively, in addition to example 1. The modification of methyl methacrylate of various ceramic particles in this example was the same as in example 1, the preparation formulation and method of the ceramic slurry were the same as in example 1, and the method for finally preparing the ceramic coating separator, the base film, the coating amount, the coating thickness, and the like were the same as in example 1. The only difference is that different ceramic particles were substituted for the alumina particles of example 1, even though the D50 of each ceramic particle was the same as the alumina particles of example 1. The details are as follows:
test 1: in this test, silica particles were used to replace the alumina particles of example 1 to prepare a silica coated membrane, which was labeled as ceramic coated membrane 1.
Test 2: in this test, aluminum nitride particles were used to replace the alumina particles of example 1 to prepare an aluminum nitride coated membrane, which was labeled as ceramic coated membrane 2.
Test 3: in this test, titanium dioxide particles were used to replace the alumina particles of example 1 to prepare a titanium dioxide coated membrane, labeled ceramic coated membrane 3.
Test 4: in the experiment, vanadium pentoxide particles are used to replace the alumina particles in example 1, and the vanadium pentoxide coating membrane is prepared and marked as a ceramic coating membrane 4.
Test 5: in this test, barium titanate particles were used to replace the alumina particles of example 1 to prepare a barium titanate coating membrane, which was labeled as ceramic coating membrane 5.
Five ceramic-coated separators prepared in this example were tested by the same test method as in example 1, and the test results are shown in table 2.
TABLE 2 results of performance testing of ceramic coatings prepared from different ceramic particles
The results in table 2 show that silica particles, aluminum nitride particles, titanium dioxide particles, vanadium pentoxide particles and barium titanate particles of the same specification can obtain the equivalent effect of the methyl methacrylate modified alumina nanosphere of example 1, namely, the liquid absorption rate and the liquid retention rate are improved, and the air permeability and the heat shrinkage performance are improved after the methyl methacrylate modified alumina nanosphere is modified.
Example 3
In this example, a test was conducted using a different modifier when modifying methyl methacrylate in addition to example 1, and the details are the same as in example 1 except that the modifier used in this example is different:
test 1: this experiment used the same amount of vinyltriethoxysilane modifier in place of the modifier of example 1.
Test 2: this experiment used the same amount of 3-methacryloxypropyl tris (trimethylsiloxy) silane modifier in place of the modifier of example 1.
Test 3: this experiment used the same amount of tetraisopropoxybis (dioctylphosphite acyloxy) titanate modifier in place of the modifier of example 1.
In this example, according to the above three experiments, different modifying agents are respectively used to prepare methyl methacrylate modified and modified alumina ceramic nanospheres labeled as ceramic particles 1 to 3, 3 kinds of ceramic particles are used to prepare ceramic slurry according to the same method as in example 1, and ceramic coating membranes are prepared according to the same method as in example 1 and labeled as ceramic coating membranes 1 to 3 in sequence.
The four ceramic coated membranes prepared in this example were tested by the same test method as in example 1, and the test results are shown in table 3.
TABLE 3 results of Performance testing of ceramic coatings prepared with different modifiers
The results in Table 3 show that vinyltriethoxysilane, 3-methacryloxypropyltris (trimethylsiloxy) silane, tetraisopropoxybis (dioctylphosphite) titanate modifiers can all be used to prepare the methyl methacrylate modified ceramic particles.
The foregoing is a more detailed description of the present application in connection with specific embodiments thereof, and it is not intended to limit the present application to the details thereof. It will be apparent to those skilled in the art from this disclosure that many more simple derivations or substitutions can be made without departing from the spirit of the disclosure.
Claims (7)
1. A method for preparing ceramic particles, which is characterized by comprising the following steps: comprises the following steps of (a) carrying out,
(1) dispersing ceramic particles into absolute ethyl alcohol, then sequentially adding deionized water, ammonia water and a modifier, and uniformly stirring to obtain a mixture; performing ultrasonic stirring on the mixture, namely performing stirring at the speed of 100-120r/min for 36-60h while performing ultrasonic stirring, wherein the ultrasonic stirring conditions are as follows: ultrasonic treatment for 1s-1.5s, interval for 2s-2.5s, and frequency for 1.3-1.78 khz; after ultrasonic stirring is finished, centrifugally collecting ceramic particles, washing the ceramic particles at least once by using deionized water, and then drying the ceramic particles in vacuum at 50-80 ℃ to obtain modifier-modified ceramic particles;
(2) dispersing the ceramic particles modified by the modifier prepared in the step (1) in deionized water to prepare suspension; adding methyl methacrylate and potassium persulfate into deionized water to prepare a methyl methacrylate solution; adding methyl methacrylate solution into the suspension, and carrying out reflux reaction for 5-8h under the protection of nitrogen; washing the obtained product with deionized water for at least three times, and then carrying out vacuum drying for 12-14h at the temperature of 60-80 ℃ to obtain ceramic particles with the surfaces modified and modified by methyl methacrylate;
in the step (1), the modifier is at least one of methacryloxypropyltrimethoxysilane, vinyltriethoxysilane, 3-methacryloxypropyltris (trimethylsiloxy) silane and tetraisopropoxybis (dioctylphosphite-oxy) titanate;
in the step (1), the weight ratio of the ceramic particles to the absolute ethyl alcohol is 1:15-1: 30; the weight ratio of the added deionized water to the ceramic particles is 1:1-2: 1; the weight ratio of the added deionized water to the ammonia water is 1:1.5-1: 2.5; the weight ratio of the modifier to the ceramic particles is 1:5-3: 5;
the weight ratio of the ceramic particles modified by the modifying agent to the deionized water in the suspension liquid in the step (2) is 1:80-1: 120; the weight ratio of the methyl methacrylate to the potassium persulfate is 60:1-40: 1; in the methyl methacrylate solution in the step (2), the weight ratio of methyl methacrylate to deionized water is 1:100-20: 100.
2. The method of claim 1, wherein: the ceramic particles are ceramic micro/nanospheres prepared from at least one of silicon dioxide, aluminum oxide, aluminum nitride, titanium dioxide, vanadium pentoxide and barium titanate.
3. Ceramic particles produced by the production method according to claim 1 or 2.
4. Use of the ceramic particles according to claim 3 for the preparation of a ceramic coating slurry or a ceramic coated separator.
5. A ceramic coating slurry using the ceramic particles of claim 3.
6. A ceramic-coated separator using the ceramic particle according to claim 3 or the ceramic coating slurry according to claim 5.
7. A battery using the ceramic-coated separator of claim 6.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010025870.XA CN111200093B (en) | 2020-01-10 | 2020-01-10 | Ceramic particle and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010025870.XA CN111200093B (en) | 2020-01-10 | 2020-01-10 | Ceramic particle and preparation method and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN111200093A CN111200093A (en) | 2020-05-26 |
| CN111200093B true CN111200093B (en) | 2022-08-12 |
Family
ID=70747366
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202010025870.XA Active CN111200093B (en) | 2020-01-10 | 2020-01-10 | Ceramic particle and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN111200093B (en) |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104112833A (en) * | 2014-06-06 | 2014-10-22 | 珠海光宇电池有限公司 | Lithium ion battery separating membrane, preparing method thereof and applications of the separating membrane |
| WO2015196854A1 (en) * | 2014-06-25 | 2015-12-30 | 江苏华东锂电技术研究院有限公司 | Composite diaphragm and preparation method therefor, and lithium-ion battery |
Family Cites Families (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US10158110B2 (en) * | 2011-07-11 | 2018-12-18 | California Institute Of Technology | Separators for electrochemical systems |
| CN105531854B (en) * | 2013-09-24 | 2017-10-31 | 东洋油墨Sc控股株式会社 | Non-aqueous secondary batteries adhesive, non-aqueous secondary batteries resin combination, non-aqueous secondary batteries barrier film, non-aqueous secondary batteries electrode and non-aqueous secondary batteries |
| CN104600229B (en) * | 2015-01-28 | 2017-03-15 | 湖北科技学院 | A kind of pottery grafting barrier film preparation method and its application in lithium battery |
| CN105047845A (en) * | 2015-06-19 | 2015-11-11 | 深圳市星源材质科技股份有限公司 | High-dielectric constant nano-composite coating diaphragm and preparation method thereof |
| CN105070862B (en) * | 2015-07-14 | 2017-04-19 | 华南理工大学 | Non-woven type power lithium battery diaphragm and preparation method thereof |
| US20190123384A1 (en) * | 2017-09-05 | 2019-04-25 | Seeo, Inc. | Surface coatings for ceramic electrolyte particles |
-
2020
- 2020-01-10 CN CN202010025870.XA patent/CN111200093B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104112833A (en) * | 2014-06-06 | 2014-10-22 | 珠海光宇电池有限公司 | Lithium ion battery separating membrane, preparing method thereof and applications of the separating membrane |
| WO2015196854A1 (en) * | 2014-06-25 | 2015-12-30 | 江苏华东锂电技术研究院有限公司 | Composite diaphragm and preparation method therefor, and lithium-ion battery |
Also Published As
| Publication number | Publication date |
|---|---|
| CN111200093A (en) | 2020-05-26 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN109841779A (en) | A kind of battery diaphragm and preparation method thereof and battery | |
| TWI252166B (en) | Process for production of composite porous film | |
| CN104409674B (en) | Composite diaphragm material and preparation method and application | |
| CN113013549B (en) | Coating material for light-weight lithium ion battery diaphragm, preparation method of coating material and light-weight lithium ion battery composite diaphragm | |
| KR102432479B1 (en) | Polymer electrolyte membrane and manufacturing method thereof | |
| CN102569700B (en) | Ceramic coating membrane and preparation method thereof | |
| CN105762317A (en) | Water-soluble polymer assisted inorganic composite diaphragm preparation method | |
| JP7207328B2 (en) | Porous film, secondary battery separator and secondary battery | |
| CN102529247A (en) | Inorganic/organic composite porous lithium battery diaphragm and preparation method thereof | |
| CN110416467B (en) | Polymer diaphragm and preparation method and application thereof, and lithium ion battery and preparation method thereof | |
| CN112151728B (en) | Lithium ion battery composite diaphragm, preparation method thereof and lithium ion battery | |
| CN110190234B (en) | Ceramic coating slurry for lithium battery diaphragm and ceramic coating diaphragm | |
| CA2824635A1 (en) | Separator for electrochemical device and process for preparing the same | |
| KR20200139769A (en) | Coating slurry for manufacturing separator, separator for electrochemical device, and method for manufacturing same | |
| CN107528038A (en) | Prepare the mixed slurry of composite diaphragm and the preparation method of composite diaphragm | |
| CN110520382A (en) | Carbon material and its manufacturing method, electricity storage device electrode material and electrical storage device | |
| CN109616605B (en) | Lithium ion battery diaphragm and preparation method thereof | |
| CN110323391B (en) | Polymer diaphragm and preparation method thereof, dispersion, lithium ion battery and preparation method thereof | |
| CN109755438B (en) | Battery diaphragm, preparation method thereof and lithium battery | |
| CN113795974A (en) | Lithium ion battery separator coated with surface treated alumina | |
| CN110690396A (en) | Lithium battery diaphragm, preparation method thereof and lithium battery | |
| KR20060023674A (en) | Manufacturing method for nanoparticle-filled phase inversion polymer electrolytes | |
| CN105408532B (en) | Fluoropolymer fibers | |
| CN111200093B (en) | Ceramic particle and preparation method and application thereof | |
| CA2823168A1 (en) | Porous membrane and process for preparing the same |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |