WO2021197134A1 - Séparateur de batterie lithium-ion et son procédé de préparation, et batterie lithium-ion - Google Patents

Séparateur de batterie lithium-ion et son procédé de préparation, et batterie lithium-ion Download PDF

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WO2021197134A1
WO2021197134A1 PCT/CN2021/082347 CN2021082347W WO2021197134A1 WO 2021197134 A1 WO2021197134 A1 WO 2021197134A1 CN 2021082347 W CN2021082347 W CN 2021082347W WO 2021197134 A1 WO2021197134 A1 WO 2021197134A1
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coating
aramid
catalyst
base film
ceramic
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PCT/CN2021/082347
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English (en)
Chinese (zh)
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郑坤
胡家玲
董佳明
单军
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比亚迪股份有限公司
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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
    • 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
    • H01M50/403—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
    • 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
    • H01M50/414—Synthetic resins, e.g. thermoplastics or thermosetting resins
    • 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
    • H01M50/434—Ceramics
    • 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
    • H01M50/443—Particulate 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
    • H01M50/446—Composite material consisting of a mixture of organic and inorganic materials
    • 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
    • H01M50/449—Separators, membranes or diaphragms characterised by the material having a layered structure
    • 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

Definitions

  • the present disclosure relates to the field of lithium ion batteries, and in particular, to a lithium ion battery separator and a preparation method thereof, and a lithium ion battery.
  • the cathode material transitions from the traditional lithium iron phosphate to the ternary electrode, and to the high nickel ternary cathode.
  • the anode material is also changing from the traditional graphite to the silicon carbon material. Transition, but high energy density means high risk, and the safety problems of lithium batteries under high-temperature thermal runaway are becoming increasingly obvious.
  • the existing ceramic coating method has increased the heat-resistant temperature of polyolefin separators from 140°C to about 150°C, at higher temperatures, the ceramic layer will be powdered and its mechanical strength cannot be maintained, which cannot prevent the positive If the negative electrode contacts, the battery will catch fire and explode. Therefore, in order to match the higher energy density of lithium batteries, the research and development of battery separators with better temperature resistance is an urgent task.
  • Patent CN106252565B discloses a four-layer composite diaphragm coated with inorganic nanoparticle coating, aramid coating and adhesive coating, which improves the temperature resistance, wettability, and tightness of contact with the electrode.
  • Patent CN107170942A discloses another composite diaphragm coated with aramid fiber and ceramic particles, which simplifies the coating process, but this oil-based mixed coating solution will cause uneven ceramic dispersion, obvious agglomeration effect and poor air permeability.
  • the diaphragm coated with inorganic nanoparticles and aramid material can have certain dimensional integrity and mechanical strength at high temperature, it cannot effectively block the rapid transmission of lithium ions at high temperature. , Unable to prevent further escalation of thermal runaway.
  • the purpose of the present disclosure is to overcome the problem of poor safety of existing lithium ion batteries, and to provide a lithium ion battery separator and a preparation method thereof, and a lithium ion battery.
  • the first aspect of the present disclosure provides a lithium ion battery separator, the separator includes a base film, the base film contains catalyst composite particles; or, the separator includes a base film and a coating, at least part of the base film The surface is covered with the coating, and the coating contains catalyst composite particles;
  • the catalyst composite particle includes an inner core and an outer shell coated on the outer surface of the inner core, the inner core contains a catalyst that can catalyze the polymerization of at least one component in the electrolyte, and the outer shell contains a thermoplastic polymer.
  • the melting point of the polymer is not higher than the melting point of the base film.
  • the coating is composed of the catalyst composite particles; or,
  • the coating also contains aramid material and/or ceramic material.
  • the coating includes an aramid coating and a ceramic coating, the aramid coating contains the aramid material and the catalyst composite particles, and the ceramic coating contains the Ceramic material; at least part of the surface of the base film is covered with the aramid coating, and the surface of the ceramic coating is optionally covered with the aramid coating.
  • the content of the catalyst is 10-50% by weight.
  • the average particle diameter of the catalyst composite particles is 50 nm-400 nm.
  • the thickness of the base film is 5 ⁇ m-40 ⁇ m, and the porosity is 20-80%; the thickness of the ceramic coating is 0.5 ⁇ m-5 ⁇ m; the thickness of the aramid coating is 0.3 ⁇ m-5 ⁇ m.
  • the catalyst that can catalyze the polymerization reaction of at least one component in the electrolyte is a catalyst that can catalyze the polymerization reaction of ethylene carbonate.
  • the catalyst that can catalyze the polymerization reaction of ethylene carbonate includes one or more of inorganic alkali metal salts, organic alkali metal salts, inorganic bases, aluminum acetylacetonate, and n-butyl titanate. kind.
  • the inorganic alkali metal salt includes one or more of sodium iodide, potassium iodide, magnesium iodide, potassium chloride, and sodium chloride;
  • the organic alkali metal salt includes potassium methoxide , One or more of sodium methoxide, potassium ethoxide and sodium ethoxide;
  • the inorganic base includes one or more of potassium hydroxide, sodium hydroxide, magnesium hydroxide and calcium hydroxide.
  • the thermoplastic polymer is a polyolefin; the melting temperature of the polyolefin is 140° C. or more; further, the polyolefin is selected from polyethylene, polypropylene, and ethylene-propylene copolymer One or more of them.
  • the material of the base film is selected from one or more of polyethylene, polypropylene, and ethylene-propylene copolymer.
  • the aramid material is selected from one or more of aramid 1414, aramid 1313 and modified aramid 1414; the weight average molecular weight of the aramid material is 5000-320,000 ;
  • the ceramic material is selected from one or more of aluminum oxide, aluminum hydroxide, silicon dioxide, titanium dioxide, zirconium dioxide, magnesium oxide, zinc oxide, and barium oxide; the average particle size of the ceramic material is 10 nm- 500nm.
  • a second aspect of the present disclosure provides a method for preparing the lithium ion battery separator provided in the first aspect of the present disclosure, the method including:
  • thermoplastic polymer is coated on the surface of the catalyst to obtain the catalyst composite particles; the catalyst composite particles are mixed with the molten base membrane slurry, and the porous membrane is prepared by the melt stretching method or the thermally induced phase separation method, Obtain a base film containing the catalyst composite particles; or,
  • thermoplastic polymer is coated on the surface of the catalyst to obtain the catalyst composite particles; the slurry containing the catalyst composite particles is coated on the base film and dried to obtain the membrane.
  • a third aspect of the present disclosure provides a lithium ion battery, which includes the lithium ion battery separator provided in the first aspect of the present disclosure or the lithium ion battery separator obtained by the method of the second aspect of the present disclosure.
  • the lithium ion battery separator of the present disclosure contains composite catalyst particles with a core-shell structure, which can have a catalytic effect when the battery is thermally out of control, thereby effectively cutting off the energy transfer in the battery, so that the The lithium ion battery of the disclosed separator not only has higher safety and a wider safe use temperature range, but also has a good capacity retention rate.
  • Fig. 1 is an SEM photograph of a cross section of the diaphragm prepared in Example 1 of the present disclosure (magnification is 1000 times);
  • Figure 2 is an SEM photograph of the aramid coating on the surface of the diaphragm prepared in Example 1 of the present disclosure (magnification of 5000 times).
  • the first aspect of the present disclosure provides a lithium ion battery separator, the separator includes a base film, the base film contains catalyst composite particles; or, the separator includes a base film and a coating, at least part of the surface of the base film is covered with a coating, Containing the catalyst composite particles;
  • the catalyst composite particle includes a core and a shell covering the outer surface of the core.
  • the core contains a catalyst that can catalyze the polymerization of at least one component in the electrolyte.
  • the shell contains a thermoplastic polymer whose melting point is not high. At the melting point of the base film.
  • the coating may be applied to one or both sides of the base film, for example, the coating may be applied to both sides of the base film; on the same surface, the coating may cover part of the base film or the entire base film, for example, the coating covers the entire base film.
  • the lithium ion battery separator of the present disclosure contains catalyst composite particles in which the catalyst core is completely covered by a thermoplastic polymer shell. Below the safe temperature for use of lithium ion batteries, the casing protects the catalyst from contact with the electrolyte, which can prevent the catalyst from absorbing moisture and deterioration due to contact between the two and affecting the lithium ion transmission, so that it has a good capacity retention rate.
  • the temperature of the lithium-ion battery is above the safe temperature for battery use (for example, the temperature when the battery is thermally out of control)
  • the outer shell of the catalyst composite particles melts, and the catalyst core is exposed to the electrolyte, which can catalyze at least one of the electrolytes.
  • These components undergo polymerization reaction, consume electrolyte, and can cut off energy transmission without additional initiator, which can effectively improve the safe use temperature range of the separator and the safety performance of the lithium ion battery.
  • the coating is composed of catalyst composite particles, that is, the coating is a catalyst coating
  • the membrane may include a base film and a catalyst coating
  • the catalyst coating may contain catalyst composite particles, and at least part of the base film is covered with a catalyst coating.
  • the coating also contains aramid material and/or ceramic material. That is, the coating includes an aramid coating and/or a ceramic coating, and the separator may include a base film, an aramid coating and/or a ceramic coating.
  • the diaphragm includes a base film and an aramid coating, and the aramid coating contains aramid material and catalyst composite particles; in a second specific embodiment, the diaphragm includes a base film and a ceramic coating, The ceramic coating contains ceramic material and catalyst composite particles; in the third specific embodiment, the diaphragm includes a base membrane, an aramid coating and a ceramic coating, when the aramid coating and the ceramic coating are located on the same side of the base membrane , The aramid coating is covered on at least part of the ceramic coating, the aramid coating contains aramid material and catalyst composite particles; when the aramid coating and the ceramic coating are located on different sides of the base film, the aramid coating and At least one of the ceramic coatings contains
  • the aramid fiber in the aramid coating in the diaphragm and the ceramic skeleton of the ceramic coating have a synergistic effect, which can make the diaphragm have a smaller thermal shrinkage rate, better air permeability, and It has higher strength at high temperature.
  • the coating includes an aramid coating and a ceramic coating.
  • the aramid coating contains an aramid material and catalyst composite particles; the ceramic coating contains a ceramic material.
  • one side of the base film is covered with a ceramic coating, and the other side is covered with an aramid coating; in the second specific embodiment, one side of the base film is covered with a ceramic coating, and the other side is covered with a ceramic coating.
  • the aramid coating is coated on at least part of the ceramic coating; in a third specific embodiment, one side of the base film is covered with a ceramic coating, and the other side is uncoated, and the aramid coating is covered On at least part of the ceramic coating; in the fourth specific embodiment, both sides of the base film are respectively covered with ceramic coatings, and the aramid coating is covered on at least part of the ceramic coating.
  • the content of the catalyst can vary within a relatively large range.
  • the content of the catalyst is 10-50% by weight.
  • the content of the catalyst is 20-30% by weight.
  • lithium-ion battery separators have higher safety performance.
  • the average particle diameter of the catalyst composite particles can vary within a relatively large range.
  • the average particle diameter of the catalyst composite particles is 50 nm-400 nm.
  • the average particle size of the catalyst composite particles is 100 nm-200 nm.
  • the thickness of the base film may be 5 ⁇ m-40 ⁇ m, and the porosity may be 20-80%. In a specific embodiment of the present disclosure, the thickness of the base film may be 10 ⁇ m-35 ⁇ m, and the porosity may be 25-75%.
  • the thickness of the ceramic coating may be 0.5 ⁇ m-5 ⁇ m. In an embodiment of the present disclosure, the thickness of the ceramic coating may be 1 ⁇ m-3 ⁇ m; the thickness of the aramid coating may be 0.3 ⁇ m-5 ⁇ m. In one embodiment, the thickness of the aramid coating may be 1 ⁇ m-3 ⁇ m.
  • each layer of the separator within the above range is appropriate, which can make the separator have better strength, and the lithium ion battery containing the separator of the present disclosure has higher safety.
  • the material of the base film can be conventionally used by those skilled in the art.
  • the material of the base film can be selected from one or more of polyethylene, polypropylene, and ethylene-propylene copolymer.
  • aramid materials are conventionally used by those skilled in the art, such as one or more selected from aramid 1414, aramid 1313, and modified aramid 1414.
  • the weight average molecular weight of the aramid material is not specifically limited. In an embodiment of the present disclosure, the weight average molecular weight of the aramid material is 5000-320,000.
  • the catalyst that can catalyze the polymerization reaction of at least one component in the electrolyte may be a catalyst that can catalyze the polymerization reaction of ethylene carbonate.
  • the outer shell of the catalyst composite particles melts, and the catalyst core is exposed to the electrolyte to catalyze the polymerization reaction of ethylene carbonate in the electrolyte, and release carbon dioxide gas, topping the battery.
  • the explosion-proof valve releases energy.
  • the catalyst that can catalyze the polymerization reaction of ethylene carbonate may include one or more of inorganic alkali metal salts, organic alkali metal salts, inorganic bases, aluminum acetylacetonate, and n-butyl titanate.
  • the inorganic alkali metal salt may include one or more of sodium iodide, potassium iodide, magnesium iodide, potassium chloride, and sodium chloride;
  • the organic alkali metal salt may include potassium methoxide, sodium methoxide , One or more of potassium ethoxide and sodium ethoxide;
  • the inorganic base may include one or more of potassium hydroxide, sodium hydroxide, magnesium hydroxide and calcium hydroxide.
  • the thermoplastic polymer may be polyolefin; the melting temperature of polyolefin may be above 140°C. In one embodiment of the present disclosure, the melting temperature of polyolefin is 140-200°C. In one embodiment, the melting temperature of the polyolefin is 145-155°C. In yet another embodiment of the present disclosure, the polyolefin may be selected from one or more of polyethylene, polypropylene, and ethylene-propylene copolymer.
  • ceramic materials are well-known to those skilled in the art, and may include, for example, one or more of aluminum oxide, aluminum hydroxide, silicon dioxide, titanium dioxide, zirconium dioxide, magnesium oxide, zinc oxide, and barium oxide. Species; the average particle size of the ceramic material can be 10nm-500nm.
  • a second aspect of the present disclosure provides a method for preparing the lithium ion battery separator provided in the first aspect of the present disclosure, the method including:
  • thermoplastic polymer is coated on the surface of the catalyst to obtain the catalyst composite particles; the catalyst composite particles are mixed with the molten base film slurry, and the porous membrane is prepared by the melt stretching method or the thermally induced phase separation method to obtain the catalyst composite particles.
  • Basement membrane or,
  • thermoplastic polymer is coated on the surface of the catalyst to obtain catalyst composite particles; the slurry containing the catalyst composite particles is coated on the base film and dried to obtain a diaphragm.
  • the method of the present disclosure can prepare a catalyst that can effectively prevent thermal runaway of the lithium ion battery and improve the safety performance of the lithium ion battery.
  • the coating method may include one or more of fluidized bed spray granulation, stirring method, extrusion granulation method, boiling granulation method and hot melt molding method.
  • fluidized bed spray granulation refers to spraying molten thermoplastic polymer on the surface of catalyst particles in a fluidized state in a fluidized bed at a certain temperature to obtain catalyst composite particles.
  • the stirring method, the extrusion granulation method, the boiling granulation method and the hot melt molding method are well known to those skilled in the art, and will not be repeated here.
  • the temperature of the granulation treatment can be selected according to the melting temperature of the thermoplastic polymer, which will not be repeated here.
  • the method may include: dissolving the aramid material in the first solvent in the presence of a co-solvent to obtain a first solution; dispersing the catalyst composite particles in the first solution to obtain a slurry; Cover the base film with or without ceramic coating.
  • the aramid material and the co-solvent are added to the first solvent, heated and stirred at 40-90°C for 2-4 hours to obtain the first solution, and then the catalyst composite particles are added to the first solution and mixed evenly.
  • the way of stirring For example, it can be ultrasonic stirring or mechanical stirring.
  • stirring parameters There are no restrictions on the stirring parameters, and can be selected according to actual needs, as long as it can be fully mixed and uniform.
  • the following steps are adopted to prepare a base film covered with a ceramic coating: in the presence of a dispersant, the ceramic material and the binder are dispersed in deionization to obtain a ceramic casting liquid; and the ceramic casting liquid is coated on Remove the deionized water on one or both sides of the base film to obtain a base film covered with a ceramic coating.
  • the average particle size of the ceramic material can be varied within a relatively large range.
  • the ceramic material is a nano-scale ceramic material, for example, it can be 10-500 nm.
  • the dispersant is well known to those skilled in the art, and may include, for example, one or more of polyvinyl alcohol, polyacrylic acid, sodium salt, and carboxymethyl cellulose.
  • the binder is conventionally used by those skilled in the art, for example, it may include polyacrylate.
  • the binder includes polyethyl acrylate, polybutyl acrylate, and ⁇ -cyanoacrylic acid. One or more of esters.
  • the method for removing the deionized water is not specifically limited.
  • the ceramic casting liquid can be coated on one or both sides of the base film, and then dried to remove the deionized water.
  • the amount of dispersant, binder and deionized water can be selected according to actual needs, as long as the ceramic casting liquid with stable properties can be obtained, and the specific amount will not be repeated here.
  • the ceramic material and the dispersant are added to deionized water, the two are uniformly mixed by mechanical stirring, and then the binder is added for stirring and dispersing to obtain a ceramic casting liquid.
  • the content of the co-solvent may be 1-10% by weight
  • the content of the aramid material may be 1-6% by weight
  • the content of the catalyst composite particles may be 1-10% by weight .
  • the content of the co-solvent is 2 to 5% by weight
  • the content of the aramid material is 3 to 6% by weight
  • the content of the catalyst composite particles is 3 to 6% by weight.
  • the co-solvent is well-known to those skilled in the art, and may include, for example, one or more of sodium chloride, calcium chloride, lithium chloride, and sodium benzoate.
  • the first solvent is well-known to those skilled in the art, and may include, for example, N,N-dimethylformamide, N,N-dimethylacetamide, N-methylpyrrolidone, dimethylsulfoxide, and o-benzene.
  • One or more of dimethyl dicarboxylate and acetone One or more of dimethyl dicarboxylate and acetone.
  • a third aspect of the present disclosure provides a lithium ion battery, which may include the lithium ion battery separator provided in the first aspect of the present disclosure or a lithium ion battery separator prepared by the method provided in the second aspect of the present disclosure.
  • the lithium ion battery of the present disclosure has a wide safe use temperature range and high safety.
  • anhydrous potassium hydroxide 20 g is pulverized into nanoparticles, and simultaneously sprayed with 80 g of molten polyethylene into a low-temperature furnace (temperature 150° C.) to obtain catalyst composite particles.
  • the average particle size of the catalyst composite particles is 100 nm
  • the catalyst core is potassium hydroxide
  • the content of the catalyst in the catalyst composite particles is 20% by weight.
  • 3% by weight of modified 1414 aramid (weight average molecular weight is 100,000) and 3% by weight of anhydrous calcium chloride are dissolved in N-methylpyrrolidone (NMP) , Stirring at room temperature for 2 hours, then heating to 90°C and stirring for 2 hours, completely dissolving and cooling to room temperature, adding 1% by weight of the composite catalyst particles prepared in step (1), and ultrasonically dispersing for 20 minutes to obtain an aramid film casting solution ( Namely slurry).
  • NMP N-methylpyrrolidone
  • the thickness of the single-sided ceramic coating in the diaphragm is 2 ⁇ m, and the thickness of the single-sided aramid coating is 3 ⁇ m.
  • the surface morphology of the diaphragm prepared in this example is observed with a scanning electron microscope (SEM, JEOL, JSM-7600FE), where, Figure 1 is a SEM photo of the cross-section of the diaphragm. The photo shows the structure of the coating on one side of the base membrane. The photo shows the base membrane, ceramic coating and aramid coating, ceramic coating and aramid in order from top to bottom. The coating has a rich pore structure.
  • Figure 2 shows the SEM image of the aramid coating on the surface of the diaphragm.
  • the diaphragm was prepared by the same method as in Example 1, except that in step (1), the amount of anhydrous potassium hydroxide was 5 g.
  • the content of the catalyst in the composite catalyst particles is 6% by weight.
  • the diaphragm was prepared by the same method as in Example 1, except that in step (1), the amount of anhydrous potassium hydroxide was 5 g, and the amount of polyethylene was 20 g.
  • the average particle size of the composite catalyst particles is 30 nm.
  • the diaphragm was prepared by the same method as in Example 1, except that there was no step (3) and no ceramic casting liquid was coated on the base film in step (4).
  • the diaphragm was prepared by the same method as in Example 1, except that in step (3), the aramid casting liquid was coated on the ceramic surface of the diaphragm with a 120 ⁇ m slit scraper using a doctoring method, and soaked in water for 3 minutes at room temperature. Place it in an oven at 50°C for 2 hours and then take it out; then use the same method to coat the aramid fiber on the other side, and after baking in an oven at 50°C for 2 hours, the separator of the present disclosure is obtained. Among them, the thickness of the aramid coating of the separator is 6 ⁇ m.
  • 5% by weight of modified 1414 aramid (weight average molecular weight is 100,000) and 5% by weight of anhydrous calcium chloride are dissolved in N-methylpyrrolidone (NMP) , Stirring at room temperature for 2 hours, then heating to 90°C and stirring for 2 hours, completely dissolving and cooling to room temperature, adding 1% by weight of the composite catalyst particles prepared in step (1), and ultrasonically dispersing for 20 minutes to obtain an aramid film casting solution.
  • NMP N-methylpyrrolidone
  • 3% by weight of modified 1414 aramid (weight average molecular weight is 100,000) and 3% by weight of anhydrous calcium chloride are dissolved in N-methylpyrrolidone (NMP) , Stirring at room temperature for 2 hours, then heating to 90°C and stirring for 2 hours, completely dissolving and cooling to room temperature, adding 5 wt% of the composite catalyst particles prepared in step (1), and ultrasonically dispersing for 20 minutes to obtain an aramid film casting solution.
  • NMP N-methylpyrrolidone
  • Example 2 Using the same method as in Example 1, 20g of catalyst composite particles were prepared, and a porous film was prepared by melt stretching. After mixing it with 200g of molten polyolefin slurry, it was mixed into a homogeneous melt at 140°C. Annealing and crystallization treatment at °C to obtain a hard elastic film, the hard elastic film is cold stretched by 6-30%, and then hot stretched at 90-130°C for 50-80%, and finally heat-set to obtain a polyolefin base containing catalyst particles The film has a thickness of 11 ⁇ m.
  • a commercially available PE base film with a thickness of 9 ⁇ m is used as the diaphragm, and the manufacturer is Cangzhou Mingzhu.
  • the diaphragm was prepared by the same method as in Example 1, except that there was no step (1) and step (2).
  • step (4) the base film was not coated with aramid casting liquid to prepare the diaphragm.
  • the base film is only covered with a ceramic coating, and the thickness of the ceramic coating is the same as in Example 1.
  • the diaphragm was prepared by the same method as in Example 1, except that there was no step (1), in step (2), the catalyst (potassium hydroxide) particles without a coating shell were used as the raw material to prepare the aramid cast film
  • the thickness of the ceramic coating and the aramid coating are the same as in Example 1, and the average particle size of the catalyst particles is the same as the average particle size of the composite catalyst particles in Example 1.
  • the diaphragms (with an area of 5 ⁇ 5 cm) prepared in the Examples and Comparative Examples were subjected to isothermal heat treatment at 150°C and 180°C in a constant temperature oven for 2h and 1h, respectively, and the transverse (TD) and longitudinal (MD) values were calculated respectively. Heat shrinkage.
  • the air permeability meter of model 4110N is used for testing. Test the time for 100 mL of air to pass through a diaphragm with an area of 1.0 square inch under a certain pressure.
  • the separators prepared in Examples 1-9 and Comparative Examples 1-3 of the present application, the positive electrode, the negative electrode, and the electrolyte are respectively prepared into button batteries, wherein the positive electrode is lithium cobaltate, the negative electrode is graphite, and the electrolyte is LB65.
  • the lithium-ion batteries of Comparative Examples 1-3 cannot guarantee that the lithium-ion batteries have good safety while also having a good capacity retention rate.
  • the safety of the lithium-ion batteries of Comparative Example 1 Poor performance; the battery impedance of comparative example 2 is not within the range of 80-150 ⁇ at 150°C, indicating that its safety is also poor; although the lithium ion battery of comparative example 3 has good safety, its capacity retention rate is poor .
  • the lithium ion batteries of Examples 1-9 have good safety, they also have a good capacity retention rate.
  • the lithium ion battery containing the separator of the present disclosure has good safety performance and capacity retention rate at the same time.

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  • Cell Separators (AREA)

Abstract

La présente invention concerne un séparateur de batterie lithium-ion et son procédé de préparation, et une batterie lithium-ion. Le séparateur comprend un séparateur de base, qui contient des particules composites de catalyseur; ou bien le séparateur comprend un séparateur de base et un revêtement, au moins une partie d'une surface du séparateur de base étant revêtue d'un revêtement, ledit revêtement contenant des particules composites de catalyseur. Les particules composites de catalyseur comprennent un noyau et une enveloppe revêtue sur une surface externe du noyau ; le noyau contient un catalyseur qui peut catalyser au moins un composant dans un électrolyte pour subir une polymérisation; et l'enveloppe contient un polymère thermoplastique, le point de fusion du polymère thermoplastique n'étant pas supérieur au point de fusion du séparateur de base.
PCT/CN2021/082347 2020-03-31 2021-03-23 Séparateur de batterie lithium-ion et son procédé de préparation, et batterie lithium-ion WO2021197134A1 (fr)

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CN116345063B (zh) * 2023-05-31 2023-08-29 合肥长阳新能源科技有限公司 涂覆型锂电池隔膜及其制备方法和锂电池

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