CN111403665A - Ceramic-coated lithium battery diaphragm and preparation method thereof - Google Patents
Ceramic-coated lithium battery diaphragm and preparation method thereof Download PDFInfo
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- 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
- H01M50/446—Composite material consisting of a mixture of organic and inorganic materials
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
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- 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
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- 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
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- 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
- H01M50/431—Inorganic material
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M2200/00—Safety devices for primary or secondary batteries
- H01M2200/10—Temperature sensitive devices
- H01M2200/106—PTC
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Abstract
The invention relates to the technical field of lithium battery diaphragms, and provides a ceramic coating lithium battery diaphragm and a preparation method thereof, wherein the ceramic coating lithium battery diaphragm comprises a base film, one side or two sides of the base film are coated with a PTC material layer, one side of the PTC material layer, which is far away from the base film, is coated with ceramic slurry, and the PTC material layer is composed of the following raw materials in parts by weight: 40-50 parts of epoxy resin, 5-10 parts of carbon black, 0.6-1.2 parts of bentonite, 28-42 parts of curing agent and 70-90 parts of propylene glycol ester, wherein the ceramic slurry comprises 30-40 parts of modified silicon dioxide, 4.5-6.5 parts of binder, 0.4-0.6 part of thickening agent and 50-60 parts of solvent.
Description
Technical Field
The invention relates to the technical field of lithium battery diaphragms, in particular to a ceramic coating lithium battery diaphragm and a preparation method thereof.
Background
The currently used lithium battery diaphragm is mainly a polyolefin diaphragm which has good chemical stability and mechanical strength, but with higher and higher requirements on the lithium battery, the polyolefin diaphragm has some defects, for example, the melting point of polyethylene is 135 ℃, the melting point of polypropylene is 165 ℃, when the temperature is sharply increased due to the internal short circuit of the battery, the diaphragm is volatilized from the mechanical integrity, large-area shrinkage occurs to cause the contact of a positive electrode and a negative electrode, and the battery is exposed to the danger of combustion and explosion at high temperature.
In view of this, the existing improvement method is to coat a ceramic slurry layer on the surface of the lithium battery separator, thereby improving the structural stability, thermal stability and safety of the separator material. Patent numbers: 201110379586.3 discloses a lithium ion battery diaphragm and a high temperature thermal stable lithium ion battery, which comprises a polyolefin microporous film as a base layer, wherein a nano ceramic material coating is made on one side surface or two side surfaces of the polyolefin microporous film, and the nano ceramic material coating is composed of deionized water, a binder aqueous solution, a solvent and ceramic powder. Compared with the conventional diaphragm, the lithium ion battery diaphragm prepared by the invention has better insulating property, and particularly avoids thermal runaway of a lithium battery caused by further internal insulating property damage caused by thermal shrinkage of the conventional diaphragm at high temperature, so that the high-temperature thermal stability of the lithium ion battery is improved, and the safety and reliability of the lithium ion battery are improved. However, the nano ceramic material coating simply suspends the ceramic powder in the whole system, the surface of the ceramic powder is not treated, the ceramic powder has larger specific surface energy and is easy to agglomerate, the surface of the ceramic powder is generally hydrophilic, and the polyolefin film is a hydrophobic material, so that the uniformity of the ceramic powder coating is poor, the bonding force between the ceramic powder and the polyolefin microporous film is weak, the phenomenon of powder falling is easy to occur, and the service performance of the ceramic coating diaphragm in a lithium battery is influenced.
Disclosure of Invention
Therefore, aiming at the above content, the invention provides a ceramic coating lithium battery diaphragm and a preparation method thereof, and solves the problem that the lithium battery diaphragm in the prior art has poor thermal stability and further affects the safety of a lithium battery.
In order to achieve the purpose, the invention is realized by the following technical scheme:
the ceramic coating lithium battery diaphragm comprises a base film, wherein a PTC material layer is coated on one surface or two surfaces of the base film, a ceramic slurry is coated on one surface, away from the base film, of the PTC material layer, and the PTC material layer is composed of the following raw materials in parts by weight: 40-50 parts of epoxy resin, 5-10 parts of carbon black, 0.6-1.2 parts of bentonite, 28-42 parts of curing agent and 70-90 parts of propylene glycol ester, wherein the ceramic slurry comprises 30-40 parts of modified silicon dioxide, 4.5-6.5 parts of binder, 0.4-0.6 part of thickening agent and 50-60 parts of solvent,
the preparation method of the modified silicon dioxide comprises the following steps: stirring and mixing the nano silicon dioxide, the triacetoxy vinyl silane and the ethanol for 20-40min, wherein the mass ratio of the nano silicon dioxide to the triacetoxy vinyl silane to the ethanol is (2.4-3.2): 1.5-2: 20-40, then ultrasonically oscillating for 30-60min, filtering, and vacuum drying to obtain white powder; adding white powder and methyl acrylate monomer into a reactor filled with toluene, and introducing nitrogen into the reactor, wherein the mass ratio of the white powder to the methyl acrylate monomer to the toluene is 2-3: 0.9-1.8: 28-42, adding an initiator with the mass fraction of 1-3% of methyl acrylate monomer, reacting at the constant temperature of 65-80 ℃ for 3-5h, and obtaining the modified silicon dioxide after the reaction is finished.
The further improvement is that: the base film is any one of a polyethylene film, a polypropylene/polyethylene/polypropylene composite film and a polyvinylidene fluoride film.
The further improvement is that: the initiator is any one of tert-butyl peroxybenzoate, dibenzoyl peroxide and dicumyl peroxide.
The further improvement is that: the binder is any one of polyvinyl alcohol, carboxymethyl cellulose, styrene butadiene rubber and polytetrafluoroethylene.
The further improvement is that: the thickening agent is any one of sodium polyacrylate, fatty alcohol and polyurethane thickening agent, and the solvent is any one of deionized water, N-methylpyrrolidone, N-dimethylformamide, ethanol and dimethyl sulfoxide.
The further improvement is that: the curing agent is any one of isophorone diamine, 2-methylimidazole and polyether amine curing agents.
A preparation method of a ceramic coating lithium battery diaphragm comprises the following steps:
(1) preparation of the PTC material layer: weighing raw materials according to the formula, stirring and mixing epoxy resin, carbon black, bentonite and propylene glycol ester for 30-40min, adding a curing agent, continuously stirring and mixing for 25-45min, then coating the mixture on one side or two sides of a base film, and curing for 10-20min at 90-120 ℃ to form a PTC material layer;
(2) preparing ceramic slurry: weighing the modified silicon dioxide, the binder, the thickener and the solvent in parts by weight, stirring and mixing for 1-3h, and uniformly mixing to obtain ceramic slurry;
(3) preparing a ceramic coating lithium battery diaphragm: and coating the prepared ceramic slurry on a PTC material layer, and drying to obtain the ceramic-coated lithium battery diaphragm.
The further improvement is that: the coating mode is knife coating, roll coating, spray coating or gravure coating.
By adopting the technical scheme, the invention has the beneficial effects that:
1. when a certain temperature (curie temperature) is exceeded, the resistance of the PTC material increases in a stepwise manner with increasing temperature. According to the lithium battery diaphragm prepared by the invention, the single surface or double surfaces of the base film are coated with the PTC material layer, and the PTC material layer is composed of the following raw materials in parts by weight: 40-50 parts of epoxy resin, 5-10 parts of carbon black, 0.6-1.2 parts of bentonite, 28-42 parts of curing agent and 70-90 parts of propylene glycol ester, when the internal temperature of the lithium battery is out of control and is within the range of 130-160 ℃, the resistance of the PTC material is rapidly increased, an ion transmission channel is cut off, the reaction speed of the battery is greatly reduced, and the safety performance of the battery is effectively improved. When the internal temperature of the battery returns to normal, the resistance of the PTC material becomes small again, and the battery is charged and discharged normally again. The melting point of the polyethylene diaphragm is 135 ℃, the melting point of the polypropylene is 165 ℃, the diaphragm starts to shrink thermally after reaching the melting point, so that the anode and the cathode are in contact short circuit, the PTC material of the invention shows obvious PTC effect in the range of 130-160 ℃, and in the temperature range, the lithium battery diaphragm starts to shrink thermally just before the PTC material layer can prevent the internal temperature of the battery from further rising, so that the large-area thermal shrinkage of the diaphragm occurs, the thermal shrinkage performance of the diaphragm is improved, and the overall service life of the battery is prolonged. The stability of the PTC material can be improved by adding a small amount of bentonite into the PTC material.
2. The surface of the nano silicon dioxide contains a large amount of hydroxyl and unsaturated bonds, so that silicon dioxide particles are easy to agglomerate, the surface energy of the nano silicon dioxide particles is high, the nano silicon dioxide particles are in a thermodynamic unstable state, and the nano silicon dioxide particles are difficult to uniformly disperse in a solvent, so that the nano silicon dioxide particles cannot play a good role. According to the invention, the surface of the silicon dioxide is modified, firstly, vinyl is introduced to the surface of silicon dioxide particles, and then the silicon dioxide particles are copolymerized with methyl acrylate monomer under the action of an initiator, so that the obtained modified silicon dioxide can be uniformly dispersed in a solvent, the formed ceramic slurry has good adhesion with a PTC material layer, and the silicon dioxide is not easy to fall off after being coated. The high-temperature-resistant ceramic slurry is coated on the base film, so that the heat resistance of the diaphragm is improved, the heat shrinkage of the diaphragm is improved, the affinity of the diaphragm and electrolyte is enhanced, and the diaphragm has good wettability and liquid absorption rate to the electrolyte. The ceramic slurry comprises 30-40 parts of modified silicon dioxide, 4.5-6.5 parts of binder, 0.4-0.6 part of thickener and 50-60 parts of solvent, wherein carboxymethyl cellulose is used as the binder and can also have a thickening effect to enhance the coating effect of the ceramic slurry.
In a word, when the internal temperature of the battery is too high, the ceramic slurry coated on the diaphragm can enhance the heat resistance of the diaphragm and reduce the heat shrinkage rate of the diaphragm, but when the temperature is further increased, the diaphragm can still undergo large-area heat shrinkage to cause short circuit, and the PTC material layer coated on the base film can prevent the temperature from further increasing and avoid the short circuit of the battery.
Detailed Description
The following detailed description will be provided for the embodiments of the present invention with reference to specific embodiments, so that how to apply the technical means to solve the technical problems and achieve the technical effects can be fully understood and implemented.
Unless otherwise indicated, the techniques employed in the examples are conventional and well known to those skilled in the art, and the reagents and products employed are also commercially available. The source, trade name and if necessary the constituents of the reagents used are indicated at the first appearance.
Example one
The utility model provides a pottery coating lithium battery diaphragm, pottery coating lithium battery diaphragm includes the polypropylene membrane, the two sides of polyethylene film are coated with the PTC material layer, the one side coating that the polyethylene film is kept away from in the PTC material layer has ceramic thick liquids, the PTC material layer comprises the raw materials of following parts by weight: 40 parts of epoxy resin, 5 parts of carbon black, 0.6 part of bentonite, 28 parts of isophorone diamine and 70 parts of propylene glycol ester, wherein the ceramic slurry is prepared from the following raw materials in parts by weight: 30 parts of modified silicon dioxide, 4.5 parts of carboxymethyl cellulose, 0.4 part of sodium polyacrylate and 5 parts of deionized water, wherein the preparation method of the modified silicon dioxide comprises the following steps: mixing the components in a mass ratio of 2.4: 1.5: stirring and mixing 20 parts of nano silicon dioxide, triacetoxyvinylsilane and ethanol for 20min, then carrying out ultrasonic oscillation for 30min, filtering, and carrying out vacuum drying to obtain white powder; adding white powder and methyl acrylate monomer into a reactor filled with toluene, and introducing nitrogen into the reactor, wherein the mass ratio of the white powder to the methyl acrylate monomer to the toluene is 2: 0.9: 28, adding tert-butyl peroxybenzoate with the mass fraction of 1% of methyl acrylate monomer, reacting at the constant temperature of 65 ℃ for 5 hours, and obtaining the modified silicon dioxide after the reaction is finished.
A preparation method of a ceramic coating lithium battery diaphragm comprises the following steps:
(1) preparation of the PTC material layer: weighing the raw materials in parts by weight according to a formula, stirring and mixing epoxy resin, carbon black, bentonite and propylene glycol ester for 30min, adding isophorone diamine, continuously stirring and mixing for 25min, then rolling the mixture onto two surfaces of a polypropylene film with the thickness of 16 mu m, and curing the mixture for 10min at 90 ℃ to form a PTC material layer with the thickness of 1 mu m;
(2) preparing ceramic slurry: weighing modified silicon dioxide, carboxymethyl cellulose, sodium polyacrylate and deionized water in parts by weight, stirring and mixing for 1h, and uniformly mixing to obtain ceramic slurry;
(3) preparing a ceramic coating lithium battery diaphragm: and (3) rolling the prepared ceramic slurry onto a PTC material layer by roller, wherein the thickness of the ceramic slurry is 2 mu m, and drying to obtain the ceramic coated lithium battery diaphragm.
Example two
The utility model provides a pottery coating lithium battery diaphragm, pottery coating lithium battery diaphragm includes the polypropylene membrane, the two sides of polypropylene membrane are coated with the PTC material layer, the one side that the polypropylene membrane was kept away from to the PTC material layer is coated with ceramic thick liquids, the PTC material layer comprises the raw materials of following parts by weight: 45 parts of epoxy resin, 8 parts of carbon black, 0.9 part of bentonite, 35 parts of 2-methylimidazole and 80 parts of propylene glycol ester, wherein the ceramic slurry is prepared from the following raw materials in parts by weight: 35 parts of modified silicon dioxide, 5.5 parts of polyvinyl alcohol, 0.5 part of lauryl alcohol, 55 parts of N, N-dimethylformamide,
the preparation method of the modified silicon dioxide comprises the following steps: and (2) mixing the following components in percentage by mass: 1.8: stirring and mixing 30 parts of nano silicon dioxide, triacetoxyvinylsilane and ethanol for 30min, then carrying out ultrasonic oscillation for 45min, filtering, and carrying out vacuum drying to obtain white powder; adding white powder and methyl acrylate monomer into a reactor filled with toluene, and introducing nitrogen into the reactor, wherein the mass ratio of the white powder to the methyl acrylate monomer to the toluene is 2.5: 1.2: 35, adding dibenzoyl peroxide with the mass fraction of 2% of methyl acrylate monomer, reacting for 3-5h at the constant temperature of 65-80 ℃, and obtaining the modified silicon dioxide after the reaction is finished.
A preparation method of a ceramic coating lithium battery diaphragm comprises the following steps:
(1) preparation of the PTC material layer: weighing the raw materials in parts by weight according to a formula, stirring and mixing epoxy resin, carbon black, bentonite and propylene glycol ester for 35min, adding 2-methylimidazole, continuously stirring and mixing for 35min, then spraying the mixture on two surfaces of a polypropylene film with the thickness of 16 mu m, and curing for 15min at 105 ℃ to form a PTC material layer with the thickness of 2 mu m;
(2) preparing ceramic slurry: weighing modified silicon dioxide, polyvinyl alcohol, lauryl alcohol and N, N-dimethylformamide in parts by weight, stirring and mixing for 2 hours, and uniformly mixing to obtain ceramic slurry;
(3) preparing a ceramic coating lithium battery diaphragm: and spraying the prepared ceramic slurry on a PTC material layer, wherein the thickness of the ceramic slurry is 3 mu m, and drying to obtain the ceramic-coated lithium battery diaphragm.
EXAMPLE III
The ceramic coating lithium battery diaphragm comprises a polypropylene membrane, wherein PTC material layers are coated on two surfaces of the polyvinylidene fluoride membrane, ceramic slurry is coated on one surface, away from the polyvinylidene fluoride membrane, of the PTC material layer, and the PTC material layers are composed of the following raw materials in parts by weight: 50 parts of epoxy resin, 10 parts of carbon black, 1.2 parts of bentonite, 42 parts of a polyether amine curing agent and 90 parts of propylene glycol ester, wherein the ceramic slurry is prepared from the following raw materials in parts by weight: 40 parts of modified silicon dioxide, 6.5 parts of polytetrafluoroethylene, 0.6 part of polyurethane thickener and 60 parts of N-methyl pyrrolidone,
the preparation method of the modified silicon dioxide comprises the following steps: mixing the components in a mass ratio of 3.2: 2: stirring and mixing 40 parts of nano silicon dioxide, triacetoxyvinylsilane and ethanol for 40min, then carrying out ultrasonic oscillation for 60min, filtering, and carrying out vacuum drying to obtain white powder; adding white powder and methyl acrylate monomer into a reactor filled with toluene, and introducing nitrogen into the reactor, wherein the mass ratio of the white powder to the methyl acrylate monomer to the toluene is 3: 1.8: 42, adding dicumyl peroxide with the mass fraction of 3% of methyl acrylate monomer, reacting at the constant temperature of 80 ℃ for 5 hours to obtain the modified silicon dioxide after the reaction is finished.
A preparation method of a ceramic coating lithium battery diaphragm comprises the following steps:
(1) preparation of the PTC material layer: weighing the raw materials in parts by weight according to a formula, stirring and mixing epoxy resin, carbon black, bentonite and propylene glycol ester for 30-40min, adding a polyether amine curing agent, continuously stirring and mixing for 45min, coating the mixture on two surfaces of a polypropylene film with the thickness of 16 mu m by a gravure manner, and curing for 20min at 120 ℃ to form a PTC material layer with the thickness of 3 mu m;
(2) preparing ceramic slurry: weighing modified silicon dioxide, polytetrafluoroethylene, a polyurethane thickener and N-methyl pyrrolidone in parts by weight, stirring and mixing for 3 hours, and uniformly mixing to obtain ceramic slurry;
(3) preparing a ceramic coating lithium battery diaphragm: and coating the prepared ceramic slurry on a PTC material layer by a gravure way, wherein the thickness of the ceramic slurry is 4 mu m, and drying to obtain the ceramic coated lithium battery diaphragm.
Performance testing
The ceramic-coated lithium battery separators prepared in the first to third examples were subjected to heat shrinkage and liquid absorption tests, and a polypropylene film having a thickness of 16 μm was selected as a comparative example, where MD was the longitudinal direction of the separator and TD was the transverse direction of the separator, and the test results are shown in table 1.
TABLE 1
As can be seen from Table 1, the thermal shrinkage of the diaphragm prepared by coating the PTC material layer and the ceramic slurry is obviously improved, the affinity of the diaphragm with the electrolyte is enhanced, and the diaphragm has good liquid absorption rate on the electrolyte.
The above description is only an embodiment utilizing the technical content of the present disclosure, and any modification and variation made by those skilled in the art can be covered by the claims of the present disclosure, and not limited to the embodiments disclosed.
Claims (8)
1. A ceramic-coated lithium battery separator characterized by: the ceramic coating lithium battery diaphragm comprises a base film, wherein a PTC material layer is coated on one surface or two surfaces of the base film, ceramic slurry is coated on one surface, away from the base film, of the PTC material layer, and the PTC material layer is composed of the following raw materials in parts by weight: 40-50 parts of epoxy resin, 5-10 parts of carbon black, 0.6-1.2 parts of bentonite, 28-42 parts of curing agent and 70-90 parts of propylene glycol ester, wherein the ceramic slurry comprises 30-40 parts of modified silicon dioxide, 4.5-6.5 parts of binder, 0.4-0.6 part of thickening agent and 50-60 parts of solvent,
the preparation method of the modified silicon dioxide comprises the following steps: stirring and mixing the nano silicon dioxide, the triacetoxy vinyl silane and the ethanol for 20-40min, wherein the mass ratio of the nano silicon dioxide to the triacetoxy vinyl silane to the ethanol is (2.4-3.2): 1.5-2: 20-40, then ultrasonically oscillating for 30-60min, filtering, and vacuum drying to obtain white powder; adding white powder and methyl acrylate monomer into a reactor filled with toluene, and introducing nitrogen into the reactor, wherein the mass ratio of the white powder to the methyl acrylate monomer to the toluene is 2-3: 0.9-1.8: 28-42, adding an initiator with the mass fraction of 1-3% of methyl acrylate monomer, reacting at the constant temperature of 65-80 ℃ for 3-5h, and obtaining the modified silicon dioxide after the reaction is finished.
2. The ceramic coated lithium battery separator as claimed in claim 1, wherein: the base film is any one of a polyethylene film, a polypropylene/polyethylene/polypropylene composite film and a polyvinylidene fluoride film.
3. The ceramic coated lithium battery separator as claimed in claim 1, wherein: the initiator is any one of tert-butyl peroxybenzoate, dibenzoyl peroxide and dicumyl peroxide.
4. The ceramic coated lithium battery separator as claimed in claim 1, wherein: the binder is any one of polyvinyl alcohol, carboxymethyl cellulose, styrene butadiene rubber and polytetrafluoroethylene.
5. The ceramic coated lithium battery separator as claimed in claim 1, wherein: the thickening agent is any one of sodium polyacrylate, fatty alcohol and polyurethane thickening agent, and the solvent is any one of deionized water, N-methylpyrrolidone, N-dimethylformamide, ethanol and dimethyl sulfoxide.
6. The ceramic coated lithium battery separator as claimed in claim 1, wherein: the curing agent is any one of isophorone diamine, 2-methylimidazole and polyether amine curing agents.
7. A method of preparing a ceramic-coated lithium battery separator as claimed in claim 1, wherein: the method comprises the following steps:
(1) preparation of the PTC material layer: weighing raw materials according to the formula, stirring and mixing epoxy resin, carbon black, bentonite and propylene glycol ester for 30-40min, adding a curing agent, continuously stirring and mixing for 25-45min, then coating the mixture on one side or two sides of a base film, and curing for 10-20min at 90-120 ℃ to form a PTC material layer;
(2) preparing ceramic slurry: weighing the modified silicon dioxide, the binder, the thickener and the solvent in parts by weight, stirring and mixing for 1-3h, and uniformly mixing to obtain ceramic slurry;
(3) preparing a ceramic coating lithium battery diaphragm: and coating the prepared ceramic slurry on a PTC material layer, and drying to obtain the ceramic-coated lithium battery diaphragm.
8. The method of preparing a ceramic-coated lithium battery separator as claimed in claim 7, wherein: the coating mode is knife coating, roll coating, spray coating or gravure coating.
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Cited By (5)
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| CN111916635A (en) * | 2020-07-30 | 2020-11-10 | 福建巨电新能源股份有限公司 | Lithium ion battery diaphragm and preparation method thereof |
| CN111916634A (en) * | 2020-07-30 | 2020-11-10 | 福建巨电新能源股份有限公司 | PTC effect diaphragm for lithium ion battery |
| CN113725555A (en) * | 2021-09-28 | 2021-11-30 | 星恒电源(滁州)有限公司 | Lithium ion battery diaphragm and preparation method thereof |
| CN114156595A (en) * | 2021-12-02 | 2022-03-08 | 新乡市中科科技有限公司 | Composite diaphragm for semi-solid lithium battery and preparation method thereof |
| CN115473007A (en) * | 2022-09-28 | 2022-12-13 | 娄底市海天特种陶瓷有限公司 | Ceramic-based diaphragm for lithium battery of new energy automobile and preparation method of ceramic-based diaphragm |
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| CN111916634A (en) * | 2020-07-30 | 2020-11-10 | 福建巨电新能源股份有限公司 | PTC effect diaphragm for lithium ion battery |
| CN113725555A (en) * | 2021-09-28 | 2021-11-30 | 星恒电源(滁州)有限公司 | Lithium ion battery diaphragm and preparation method thereof |
| CN113725555B (en) * | 2021-09-28 | 2023-03-10 | 星恒电源(滁州)有限公司 | Lithium ion battery diaphragm and preparation method thereof |
| CN114156595A (en) * | 2021-12-02 | 2022-03-08 | 新乡市中科科技有限公司 | Composite diaphragm for semi-solid lithium battery and preparation method thereof |
| CN114156595B (en) * | 2021-12-02 | 2024-04-02 | 新乡市中科科技有限公司 | Composite diaphragm for semisolid lithium battery and preparation method thereof |
| CN115473007A (en) * | 2022-09-28 | 2022-12-13 | 娄底市海天特种陶瓷有限公司 | Ceramic-based diaphragm for lithium battery of new energy automobile and preparation method of ceramic-based diaphragm |
| CN115473007B (en) * | 2022-09-28 | 2024-01-02 | 上海意定新材料科技有限公司 | Ceramic-based diaphragm for lithium battery of new energy automobile and preparation method thereof |
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