WO2023216376A1 - Séparateur de composé métallique, son procédé de préparation et son utilisation - Google Patents

Séparateur de composé métallique, son procédé de préparation et son utilisation Download PDF

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Publication number
WO2023216376A1
WO2023216376A1 PCT/CN2022/100732 CN2022100732W WO2023216376A1 WO 2023216376 A1 WO2023216376 A1 WO 2023216376A1 CN 2022100732 W CN2022100732 W CN 2022100732W WO 2023216376 A1 WO2023216376 A1 WO 2023216376A1
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Prior art keywords
layer structure
base film
metal oxide
heat
metal compound
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PCT/CN2022/100732
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English (en)
Chinese (zh)
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庄志
郭宏伟
鲍晋珍
吴惠康
蔡裕宏
冶成良
程跃
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上海恩捷新材料科技有限公司
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Publication of WO2023216376A1 publication Critical patent/WO2023216376A1/fr

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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
    • 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
    • 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
    • H01M50/449—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 invention relates to the technical field of lithium batteries, and specifically to a metal compound separator and its preparation method and application.
  • the object of the present invention is to provide a metal compound separator, which includes a base film and a coating formed on at least one side of the base film.
  • the coating at least includes heat-resistant particles and metal oxide particles.
  • the base film thickness is 5 to 16 ⁇ m, and the coating thickness is 2 to 4 ⁇ m.
  • heat-resistant particles and metal oxide particles are mixed to form a layer structure on one side of the base film as a coating.
  • the heat-resistant particles form a first layer structure on one side of the base film, and the metal oxide particles form a second layer structure on the same side of the base film, so that the first layer structure and the second layer structure together serve as a coating.
  • the second layer structure is located on a side of the first layer structure away from the base film.
  • the heat-resistant particles form a first layer structure on one side of the base film, and the metal oxide particles form a second layer structure on the other side of the base film, so that the first layer structure and the second layer structure together serve as a coating. .
  • the base film is one or more of polyethylene and polypropylene.
  • the heat-resistant particles are one or more of alumina, boehmite, and barium sulfate.
  • the particle size of the heat-resistant particles is 50 to 500 nm.
  • the metal oxide particles are one or more of transition metal oxides and Group IVA metal oxides.
  • the metal oxide particles are one or more of manganese oxide, tin oxide, ferric oxide, and ferric oxide.
  • the particle size of the metal oxide particles is 20 to 100 nm.
  • the particle size ratio between the metal oxide particles and the heat-resistant particles is 1 : (2 to 25).
  • the coating further includes a binder.
  • the binder is one or more of polytetrafluoroethylene, polytetrafluoroethylene, polypropylene, polyethylene, and sodium carboxymethylcellulose.
  • the heat-resistant particles, metal oxide particles and binder are mixed to form a layer structure.
  • heat-resistant particles are mixed with a binder to form a first layer structure
  • metal oxide particles are mixed with a binder to form a second layer structure.
  • Another object of the present invention is to provide a lithium battery, which includes a metal compound separator, a positive electrode and a negative electrode as described above, and the metal compound separator is located between the positive electrode and the negative electrode.
  • the negative electrode is located on the side of the metal compound separator formed with the layer structure.
  • the negative electrode is located on the side of the metal compound separator where the first layer structure and the second layer structure are formed.
  • the negative electrode is located on the metal compound separator and forms a second layer. side of the structure.
  • Another object of the present invention is to provide a method for preparing a metal compound separator, which includes the following steps: mixing: mixing heat-resistant particles, metal oxide particles and solvent to obtain a dispersion; and dry coating: coating the dispersion Cover at least one side of the base film and dry to obtain a metal compound separator.
  • dry coating includes: coating the dispersion liquid on at least one side of the base film, distributing the metal oxide particles to the side of the dispersion liquid away from the base film, and drying to obtain a metal compound separator.
  • the solvent is one or more of N,N-dimethylformamide, N-methylpyrrolidone, acetonitrile, ethanol, and isopropyl alcohol.
  • the dispersion further includes a binder.
  • Another object of the present invention is to provide a method for preparing a metal compound separator, which includes the following steps: mixing: mixing heat-resistant particles and a solvent to obtain a first dispersion, and mixing metal oxide particles and a solvent to obtain a second dispersion. liquid; and dry coating: apply the first dispersion liquid and the second dispersion liquid on the same side of the base film, and dry them to obtain a metal compound separator.
  • the solvent is one or more of N,N-dimethylformamide, N-methylpyrrolidone, acetonitrile, ethanol, and isopropyl alcohol.
  • the first dispersion further includes a binder
  • the second dispersion further includes a binder
  • Another object of the present invention is to provide a method for preparing a metal compound separator, which includes the following steps: mixing: mixing heat-resistant particles and a solvent to obtain a first dispersion, and mixing metal oxide particles and a solvent to obtain a second dispersion. liquid; and dry coating: apply the first dispersion liquid on one side of the base film, apply the second dispersion liquid on the other side of the base film, and dry to obtain a metal compound separator.
  • the solvent is one or more of N,N-dimethylformamide, N-methylpyrrolidone, acetonitrile, ethanol, and isopropyl alcohol.
  • the first dispersion further includes a binder
  • the second dispersion further includes a binder
  • the metal compound separator provided by the present invention coats heat-resistant particles and metal oxide particles on the base film, so that the heat-resistant particles and metal oxide particles exert a synergistic effect to improve the electrochemical performance of the lithium battery using the separator.
  • heat-resistant particles can improve the thermal stability of the separator under high temperature conditions, reduce the thermal shrinkage rate, increase the ink splash temperature, and enhance the safety performance of the battery.
  • metal oxide particles are slightly soluble and can be deposited on the surface of the negative electrode as the lithium battery discharges. As the number of battery cycles increases or the battery operates under special environments such as high or low temperatures, the lithium dendrites formed can react chemically with the metal oxide deposited on the surface of the negative electrode to form a metal alloy.
  • a protective layer can be formed on the surface of the negative electrode to adjust the electric field on the negative electrode surface, thereby making the negative electrode Li flux uniform, inhibiting the continued formation of negative electrode lithium dendrites, and improving the cycle stability of the battery.
  • the combination of heat-resistant particles of different particle sizes and metal oxide particles can also increase the tortuosity of the micropores, thereby reducing micro-short circuits and self-discharge of the battery.
  • the heat-resistant particles can also neutralize free HF in the electrolyte to avoid battery corrosion.
  • Figure 1 is a schematic cross-sectional view showing a metal compound separator according to a first embodiment of the present invention
  • Figure 2 is a schematic cross-sectional view showing a metal compound separator according to a second embodiment of the present invention.
  • Figure 3 is a schematic cross-sectional view showing a metal compound separator according to a third embodiment of the present invention.
  • Figure 4 is a graph illustrating the battery capacity retention rates of the separators of all examples and the separators of all comparative examples after different cycles.
  • Figure 1 is a metal compound separator according to a first embodiment of the present invention. It includes a base film (1) and a coating (2).
  • the coating (2) is formed on at least one side of the base film (1) and contains a resist. Thermal particles and metal oxide particles, and the heat-resistant particles and metal oxide particles are mixed to form a layer structure (21) on one side of the base film (1) as the coating (2).
  • the thickness of the base film (1) may be, but is not limited to, 5 to 16 ⁇ m
  • the thickness of the coating layer (2) may be, but is not limited to, 2 to 4 ⁇ m.
  • examples of the base film (1) may be, but are not limited to, one or more of polyethylene and polypropylene
  • examples of heat-resistant particles may be, but are not limited to, one or more of alumina, boehmite, and barium sulfate.
  • examples of metal oxide particles can be but are not limited to one or more of transition metal oxides and IVA group metal oxides, specifically but are not limited to manganese oxide, tin oxide, ferric oxide. , one or more of ferric oxide.
  • the coating (2) may further contain a binder.
  • the binder may be but are not limited to polytetrafluoroethylene, polytetrafluoroethylene, polypropylene, and polyethylene. , one or more of sodium carboxymethylcellulose. That is to say, heat-resistant particles, metal oxide particles and binders can be mixed to form a layer structure (21) as the coating (2).
  • metal oxide particles can be deposited on the surface of the negative electrode during the discharge process of lithium batteries through their slight solubility.
  • the lithium dendrites formed can react chemically with the metal oxides deposited on the surface of the negative electrode to form a metal alloy.
  • the metal alloy expands in the negative electrode through its volume expansion.
  • a protective layer is formed on the surface to inhibit the continued formation of lithium dendrites in the negative electrode, thereby improving the cycle stability of the battery.
  • the content distribution of the metal oxide particles in the layer structure (21) can decrease from the side away from the base film (1) to the side close to the base film (1); or , the particle size of the metal oxide particles can be smaller than the particle size of the heat-resistant particles, so that during film formation, the metal oxide particles are naturally distributed toward the side of the layer structure (21) away from the base film (1), so that the metal oxide particles are
  • the content distribution of the layer structure (21) decreases from the side far away from the base film (1) to the side close to the base film (1).
  • the particle size of the heat-resistant particles may be, but is not limited to, 50 to 500 nm, and the particle size of the metal oxide particles may be, but is not limited to, 20 to 100 nm.
  • the particle diameter ratio between the metal oxide particles and the heat-resistant particles may be, but is not limited to, 1 : (2 to 25).
  • the metal compound separator according to the first embodiment of the present invention can be used in lithium batteries. More specifically, in addition to a metal compound separator, a lithium battery also contains a positive electrode and a negative electrode, and the metal compound separator is located between the positive electrode and the negative electrode. In order to facilitate the deposition of metal oxide particles on the surface of the negative electrode during the discharge process of the lithium battery, the negative electrode may be located on the side of the metal compound separator formed with the layered structure (21).
  • the preparation method of the metal compound separator according to the first embodiment of the present invention is further described below, which includes: a mixing step; and a dry coating step.
  • heat-resistant particles, metal oxide particles and solvent are mixed to obtain a dispersion.
  • a solvent can disperse the heat-resistant particles and metal oxide particles so that they can subsequently be distributed in a desired manner on one side of the base film (1).
  • the solvent can be but are not limited to N,N-dimethyl One or more of formamide, N-methylpyrrolidone, acetonitrile, ethanol, and isopropyl alcohol.
  • the dispersion may further include a binder. Under this condition, the use of solvent can further dissolve the binder.
  • the dispersion is applied to one side of the base film (1) and dried to obtain a metal compound separator.
  • coating methods may be, but are not limited to, gravure roller coating, dip coating, narrow coating or spray coating.
  • the metal oxide particles can be made Distribute to the side of the dispersion liquid away from the base film (1); alternatively, the particle size of the metal oxide particles can be smaller than the particle size of the heat-resistant particles, so that after coating, the metal oxide particles naturally move toward the dispersion liquid away from the base film (1) ) is distributed on one side.
  • Figure 2 is a metal compound separator according to a second embodiment of the present invention. It includes a base film (1) and a coating (2).
  • the coating (2) is formed on at least one side of the base film (1) and contains a resist. Thermal particles and metal oxide particles, the heat-resistant particles form a first layer structure (22) on one side of the base film (1), and the metal oxide particles form a second layer structure (23) on the same side of the base film (1) On the other hand, the first layer structure (22) and the second layer structure (23) together serve as the coating (2).
  • the thickness of the base film (1) may be, but is not limited to, 5 to 16 ⁇ m
  • the thickness of the coating layer (2) may be, but is not limited to, 2 to 4 ⁇ m.
  • examples of the base film (1) may be, but are not limited to, one or more of polyethylene and polypropylene
  • examples of heat-resistant particles may be, but are not limited to, one or more of alumina, boehmite, and barium sulfate.
  • examples of metal oxide particles can be but are not limited to one or more of transition metal oxides and IVA group metal oxides, specifically but are not limited to manganese oxide, tin oxide, ferric oxide. , one or more of ferric oxide.
  • the coating (2) may further contain a binder.
  • the binder may be but are not limited to polytetrafluoroethylene, polytetrafluoroethylene, polypropylene, and polyethylene. , one or more of sodium carboxymethylcellulose. That is to say, the heat-resistant particles and the binder can be mixed to form the first layer structure (22), and the metal oxide particles and the binder can be mixed to form the second layer structure (23), so that the first layer structure (22) and the binder can be mixed to form the second layer structure (23).
  • the second layer structure (23) together serves as coating (2).
  • metal oxide particles can be deposited on the surface of the negative electrode during the discharge process of lithium batteries through their slight solubility.
  • the lithium dendrites formed can react chemically with the metal oxides deposited on the surface of the negative electrode to form a metal alloy.
  • the metal alloy expands in the negative electrode through its volume expansion.
  • a protective layer is formed on the surface to inhibit the continued formation of lithium dendrites in the negative electrode, thereby improving the cycle stability of the battery.
  • the second layer structure (23) is located on the side of the first layer structure (22) away from the base film (1).
  • the particle size of the heat-resistant particles may be, but is not limited to, 50 to 500 nm, and the particle size of the metal oxide particles may be, but is not limited to, 20 to 100 nm.
  • the metal compound separator according to the second embodiment of the present invention can be used in lithium batteries. More specifically, in addition to a metal compound separator, a lithium battery also contains a positive electrode and a negative electrode, and the metal compound separator is located between the positive electrode and the negative electrode. In order to facilitate the deposition of metal oxide particles on the surface of the negative electrode during the discharge process of the lithium battery, the negative electrode can be located on the side of the metal compound separator where the first layer structure (22) and the second layer structure (23) are formed.
  • the preparation method of the metal compound separator according to the second embodiment of the present invention is further described below, which includes: a mixing step; and a dry coating step.
  • the heat-resistant particles and the solvent are mixed to obtain a first dispersion liquid
  • the metal oxide particles and the solvent are mixed to obtain a second dispersion liquid.
  • the use of a solvent can disperse the heat-resistant particles and the metal oxide particles so that they can subsequently be distributed in a desired manner on the same side of the base film (1).
  • the solvent can be but are not limited to N, N-dimethyl One or more of formamide, N-methylpyrrolidone, acetonitrile, ethanol, and isopropyl alcohol.
  • the first dispersion liquid may further include a binder
  • the second dispersion liquid may further include a binder. Under this condition, the use of solvent can further dissolve the binder.
  • the first dispersion liquid and the second dispersion liquid are coated on the same side of the base film (1), and dried to obtain a metal compound separator.
  • coating methods may be, but are not limited to, gravure roller coating, dip coating, narrow coating or spray coating.
  • Figure 3 is a metal compound separator according to a third embodiment of the present invention. It includes a base film (1) and a coating (2).
  • the coating (2) is formed on at least one side of the base film (1) and contains a resist. Thermal particles and metal oxide particles, the heat-resistant particles form a first layer structure (22) on one side of the base film (1), and the metal oxide particles form a second layer structure (23) on the other side of the base film (1) On the other hand, the first layer structure (22) and the second layer structure (23) together serve as the coating (2).
  • the thickness of the base film (1) may be, but is not limited to, 5 to 16 ⁇ m
  • the thickness of the coating layer (2) may be, but is not limited to, 2 to 4 ⁇ m.
  • examples of the base film (1) may be, but are not limited to, one or more of polyethylene and polypropylene
  • examples of heat-resistant particles may be, but are not limited to, one or more of alumina, boehmite, and barium sulfate.
  • examples of metal oxide particles can be but are not limited to one or more of transition metal oxides and IVA group metal oxides, specifically but are not limited to manganese oxide, tin oxide, ferric oxide. , one or more of ferric oxide.
  • the coating (2) may further contain a binder.
  • the binder may be but are not limited to polytetrafluoroethylene, polytetrafluoroethylene, polypropylene, and polyethylene. , one or more of sodium carboxymethylcellulose. That is to say, the heat-resistant particles and the binder can be mixed to form the first layer structure (22), and the metal oxide particles and the binder can be mixed to form the second layer structure (23), so that the first layer structure (22) and the binder can be mixed to form the second layer structure (23).
  • the second layer structure (23) together serves as coating (2).
  • metal oxide particles can be deposited on the surface of the negative electrode during the discharge process of lithium batteries through their slight solubility.
  • the lithium dendrites formed can react chemically with the metal oxides deposited on the surface of the negative electrode to form a metal alloy.
  • the metal alloy expands in the negative electrode through its volume expansion.
  • a protective layer is formed on the surface to inhibit the continued formation of lithium dendrites in the negative electrode, thereby improving the cycle stability of the battery.
  • the content distribution of the metal oxide particles in the second layer structure (23) can decrease from the side far away from the base film (1) to the side close to the base film (1) .
  • the particle size of the heat-resistant particles may be, but is not limited to, 50 to 500 nm, and the particle size of the metal oxide particles may be, but is not limited to, 20 to 100 nm.
  • the particle diameter ratio between the metal oxide particles and the heat-resistant particles may be, but is not limited to, 1: (2 to 25).
  • the metal compound separator according to the third embodiment of the present invention can be used in lithium batteries. More specifically, in addition to a metal compound separator, a lithium battery also contains a positive electrode and a negative electrode, and the metal compound separator is located between the positive electrode and the negative electrode. In order to facilitate the deposition of metal oxide particles on the surface of the negative electrode during the discharge process of the lithium battery, the negative electrode may be located on the side of the metal compound separator where the second layer structure (23) is formed.
  • the preparation method of the metal compound separator according to the third embodiment of the present invention is further described below, which includes: a mixing step; and a dry coating step.
  • the heat-resistant particles and the solvent are mixed to obtain a first dispersion liquid
  • the metal oxide particles and the solvent are mixed to obtain a second dispersion liquid.
  • the use of a solvent can disperse the heat-resistant particles and metal oxide particles so that they can subsequently be distributed on both sides of the base film (1) in a desired manner.
  • the solvent can be but are not limited to N, N-dimethyl One or more of formamide, N-methylpyrrolidone, acetonitrile, ethanol, and isopropyl alcohol.
  • the first dispersion liquid may further include a binder
  • the second dispersion liquid may further include a binder. Under this condition, the use of solvent can further dissolve the binder.
  • the first dispersion liquid is applied to one side of the base film (1)
  • the second dispersion liquid is applied to the other side of the base film (1)
  • Examples of coating methods may be, but are not limited to, gravure roller coating, dip coating, narrow coating or spray coating.
  • the separator in this embodiment has a base film thickness of 9 ⁇ m and a coating thickness of 2 ⁇ m.
  • alumina heat-resistant particles with a particle size of 100 nm mix alumina heat-resistant particles with a particle size of 100 nm, manganese oxide metal oxide particles with a particle size of 50 nm, PVDF binder and solvent to obtain a dispersion.
  • the solvent is N, N-dimethylformamide, N-formamide.
  • the dispersion liquid is applied to one side of the polyethylene film and then dried to obtain a separator.
  • the separator in this embodiment has a base film thickness of 9 ⁇ m and a coating thickness of 4 ⁇ m.
  • alumina heat-resistant particles with a particle size of 100 nm, a PVDF binder and a solvent are mixed to obtain a first dispersion
  • manganese oxide metal oxide particles with a particle size of 50 nm, a PVDF binder and a solvent are mixed to obtain a second dispersion.
  • the solvent is one or more of N,N-dimethylformamide, N-methylpyrrolidone, acetonitrile, ethanol, and isopropyl alcohol.
  • the first dispersion liquid is applied to one side of the polyethylene base film and then dried, and the second dispersion liquid is applied to the same side of the polyethylene base film and then dried to obtain a separator.
  • the separator in this embodiment has a base film thickness of 9 ⁇ m and a coating thickness of 3 ⁇ m.
  • alumina heat-resistant particles with a particle size of 500 nm mix alumina heat-resistant particles with a particle size of 500 nm, manganese oxide metal oxide particles with a particle size of 100 nm, PVDF binder and solvent to obtain a dispersion.
  • the solvent is N, N-dimethylformamide, N-formamide.
  • the dispersion liquid is coated on both sides of the polyethylene film and then dried to obtain a separator. Since the particle size of the aluminum oxide heat-resistant particles is much larger than the particle size of the manganese oxide metal oxide particles, when the coating is dry, the manganese oxide metal oxide particles will be distributed to the side away from the polyethylene film and float away from the polyethylene film. on one surface of the basement membrane.
  • the separator in this embodiment has a base film thickness of 9 ⁇ m and a coating thickness of 3 ⁇ m.
  • alumina heat-resistant particles with a particle size of 500 nm mix alumina heat-resistant particles with a particle size of 500 nm, manganese oxide metal oxide particles with a particle size of 20 nm, PVDF binder and solvent to obtain a dispersion.
  • the solvent is N, N-dimethylformamide, N-formamide.
  • the dispersion liquid is coated on both sides of the polyethylene film and then dried to obtain a separator. Since the particle size of the aluminum oxide heat-resistant particles is much larger than the particle size of the manganese oxide metal oxide particles, when the coating is dry, the manganese oxide metal oxide particles will be distributed to the side away from the polyethylene film and float away from the polyethylene film. on one surface of the basement membrane.
  • the separator in this embodiment has a base film thickness of 9 ⁇ m and a coating thickness of 3 ⁇ m.
  • alumina heat-resistant particles with a particle size of 50 nm mix alumina heat-resistant particles with a particle size of 50 nm, manganese oxide metal oxide particles with a particle size of 20 nm, PVDF binder and solvent to obtain a dispersion.
  • the solvent is N, N-dimethylformamide, N-formamide.
  • the dispersion liquid is coated on both sides of the polyethylene film and then dried to obtain a separator. Since the particle size of the aluminum oxide heat-resistant particles is much larger than the particle size of the manganese oxide metal oxide particles, when the coating is dry, the manganese oxide metal oxide particles will be distributed to the side away from the polyethylene film and float away from the polyethylene film. on one surface of the basement membrane.
  • the separator in this comparative example has a base film thickness of 9 ⁇ m and a coating thickness of 2 ⁇ m.
  • alumina heat-resistant particles with a particle size of 100 nm, PVDF binder and solvent to obtain a dispersion.
  • the solvent is N, N-dimethylformamide, N-methylpyrrolidone, acetonitrile, ethanol, and isopropyl alcohol. of one or more.
  • the dispersion liquid is applied to one side of the polyethylene film and then dried to obtain a separator.
  • the separator in this comparative example has a base film thickness of 9 ⁇ m and a coating thickness of 2 ⁇ m.
  • the solvent is N, N-dimethylformamide, N-methylpyrrolidone, acetonitrile, ethanol, and isopropyl alcohol. one or more of them.
  • the dispersion liquid is applied to one side of the polyethylene film and then dried to obtain a separator.
  • the separator in this comparative example has a base film thickness of 9 ⁇ m and a coating thickness of 3 ⁇ m.
  • alumina heat-resistant particles with a particle size of 100 nm mix alumina heat-resistant particles with a particle size of 100 nm, manganese oxide metal oxide particles with a particle size of 100 nm, PVDF binder and solvent to obtain a dispersion.
  • the solvent is N, N-dimethylformamide, N-formamide.
  • the dispersion liquid is coated on both sides of the polyethylene film and then dried to obtain a separator.
  • the separator in this comparative example has a base film thickness of 9 ⁇ m and a coating thickness of 3 ⁇ m.
  • alumina heat-resistant particles with a particle size of 50 nm mix alumina heat-resistant particles with a particle size of 50 nm, manganese oxide metal oxide particles with a particle size of 100 nm, PVDF binder and solvent to obtain a dispersion.
  • the solvent is N, N-dimethylformamide, N-formamide.
  • the dispersion liquid is coated on both sides of the polyethylene film and then dried to obtain a separator.
  • the separator in this comparative example has a base film thickness of 9 ⁇ m, which is only a polyethylene film.
  • the heat shrinkage rate is measured by high-temperature baking.
  • the specific test conditions are a temperature of 130°C and a test time of 1 hour.
  • TD and MD represent longitudinal heat shrinkage and transverse heat shrinkage respectively. The greater the heat shrinkage rate, the greater the heat shrinkage of the separator. Difference.
  • the peel strength is measured by an electronic universal testing machine.
  • the specific test conditions are effective length 200mm and effective width 30mm.
  • the amount of air permeability is measured by Gurley4320 air permeability meter.
  • Gurley4320 air permeability meter The specific test method is the time for 100ml of gas to pass through the diaphragm. The greater the air permeability increase, the worse the air permeability of the diaphragm.
  • the closed cell/film rupture temperature is measured using the Q400 thermomechanical analyzer of the American TA Company.
  • the specific test method is to cut the diaphragm spline in the MD and TD directions, pull the spline with a constant force, and heat the sample chamber at the same time. , the heating rate is 5°C/min, and the closing temperature and membrane rupture temperature are obtained.
  • the particle size distribution of heat-resistant particles and metal oxide particles is measured using a Mastersizer 2000 laser particle size analyzer.
  • the specific test method is to take a sample and add it to the test equipment so that its opacity reaches the test range. After ultrasonic for 60 seconds, test the particle size of the sample and record it.
  • the sample particle size results are D 10 , D 50 and D 90 .
  • the separator is configured with positive and negative electrodes to make a soft-packed battery core, and the cycle capacity retention rate is tested at 1C/25°C.
  • the separator is configured with positive and negative electrodes to make a soft-packed battery.
  • the battery is charged as required (4.2V CC-CV)
  • a 5mm high-temperature steel needle with a tip angle of 50 degrees to charge the battery from vertical to vertical at a speed of 25 ⁇ 2mm/s.
  • the direction of the battery plate is penetrated.
  • the steel needle stays in the battery for 10 minutes and then pulled out to observe the phenomenon.
  • Two batteries in each group are tested. If neither battery catches fire or explodes, it is judged that the battery in the experimental group has passed the acupuncture safety test (OK); if one battery catches fire or explodes, the battery in the experimental group is judged to have acupuncture safety. Safety test failed (NG).
  • Example 1 Comparative Example 5
  • aluminum oxide heat-resistant particles and manganese oxide metal oxide particles at the same time in the coating will increase the air permeability for 4 seconds, indicating that the aluminum oxide heat-resistant particles and manganese oxide metal oxide particles are effective for The breathable properties of the membrane create a synergistic effect.
  • Comparing Comparative Examples 1, 2, and 5 it can be seen that using only aluminum oxide heat-resistant particles in the coating will increase the battery capacity retention rate by 6%, and only using manganese oxide metal oxide particles in the coating will increase the battery capacity retention rate by 6%. Theoretically The simultaneous use of aluminum oxide heat-resistant particles and manganese oxide metal oxide particles in the coating will increase the battery capacity retention rate by 6%. However, comparing Example 1 and Comparative Example 5, it can be seen that the simultaneous use of aluminum oxide heat-resistant particles and manganese oxide metal oxide particles in the coating will increase the battery capacity retention rate by 18%, indicating that the aluminum oxide heat-resistant particles and manganese oxide metal oxide particles The particles have a synergistic effect on the capacity retention properties of separator batteries.
  • the appropriate particle size of alumina heat-resistant particles and manganese oxide metal oxide particles can prevent the particles from clogging the base film and enhance the breathability of the separator.
  • the heat-resistant aluminum oxide particles and manganese oxide metal oxide particles can increase the peeling strength and the temperature difference between the closed cells and membrane rupture through appropriate particle sizes, thereby improving the safety of the battery.
  • the appropriate particle size of alumina heat-resistant particles and manganese oxide metal oxide particles can maintain the battery capacity retention rate above 89% after 1000 cycles of the separator, indicating that the appropriate particle size can It has an inhibitory effect on the growth of lithium dendrites.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Inorganic Chemistry (AREA)
  • Cell Separators (AREA)

Abstract

L'invention concerne un séparateur de composé métallique, comprenant un film de base et un revêtement formé sur au moins un côté du film de base, le revêtement comprenant au moins des particules résistantes à la chaleur et des particules d'oxyde métallique. Un procédé de préparation du séparateur de composé métallique comprend les étapes suivantes consistant à : mélanger des particules résistantes à la chaleur, des particules d'oxyde métallique et un solvant pour obtenir un liquide de dispersion ; et revêtir au moins un côté du film de base avec le liquide de dispersion, et effectuer un séchage pour obtenir le séparateur de composé métallique. L'invention concerne en outre une batterie au lithium, comprenant le séparateur de composé métallique décrit, une électrode positive et une électrode négative, le séparateur de composé métallique étant situé entre l'électrode positive et l'électrode négative.
PCT/CN2022/100732 2022-05-09 2022-06-23 Séparateur de composé métallique, son procédé de préparation et son utilisation WO2023216376A1 (fr)

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