WO2014044040A1 - Feuille d'électrode négative composite pour batterie au lithium-ion et son procédé de préparation et batterie au lithium-ion - Google Patents

Feuille d'électrode négative composite pour batterie au lithium-ion et son procédé de préparation et batterie au lithium-ion Download PDF

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WO2014044040A1
WO2014044040A1 PCT/CN2013/073487 CN2013073487W WO2014044040A1 WO 2014044040 A1 WO2014044040 A1 WO 2014044040A1 CN 2013073487 W CN2013073487 W CN 2013073487W WO 2014044040 A1 WO2014044040 A1 WO 2014044040A1
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negative electrode
electrode sheet
lithium ion
ion battery
composite negative
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PCT/CN2013/073487
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English (en)
Chinese (zh)
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叶海林
张光辉
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华为技术有限公司
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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
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/04—Processes of manufacture in general
    • H01M4/043—Processes of manufacture in general involving compressing or compaction
    • H01M4/0435—Rolling or calendering
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/133—Electrodes based on carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • 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
    • H01M50/489—Separators, membranes, diaphragms or spacing elements inside the cells, characterised by their physical properties, e.g. swelling degree, hydrophilicity or shut down properties
    • H01M50/491—Porosity
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/139—Processes of manufacture
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/139—Processes of manufacture
    • H01M4/1393—Processes of manufacture of electrodes based on carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • 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
    • H01M50/44—Fibrous 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
    • 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
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/64—Carriers or collectors
    • H01M4/66—Selection of materials
    • H01M4/661—Metal or alloys, e.g. alloy coatings
    • 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
    • H01M50/46—Separators, membranes or diaphragms characterised by their combination with electrodes
    • 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 field of lithium ion batteries, and in particular to a composite negative electrode sheet for a lithium ion battery, a preparation method thereof and a lithium ion battery. Background technique
  • Lithium-ion batteries have been widely used in mobile phones, notebook computers, etc. due to their advantages of light weight, small size, high operating voltage, high energy density, high output power, high charging efficiency and no memory effect.
  • a lithium ion battery usually consists of a positive electrode sheet, a negative electrode sheet, a separator, an electrolyte, and an outer casing.
  • the separator is mainly a commercially available commercial polyethylene (PE) film or a polypropylene (PP) film having a thickness of 20 to 40 ⁇ m, a porosity of about 40%, and a separator interval of the positive electrode and the negative electrode.
  • PE polyethylene
  • PP polypropylene
  • the preparation method of the existing lithium ion battery is generally prepared by separately preparing a positive electrode sheet, a negative electrode sheet and a separator, and then winding the separator and the positive and negative electrode sheets, after being assembled and packaged, injecting and sealing, finally activating and performing performance test.
  • the separator is usually a light, soft and thin film, which is not easily aligned with the positive and negative pole pieces during the winding assembly process, and is often liable to cause short circuit between the positive and negative pole pieces, and at the same time, in the winding During the assembly process, tension is easily generated to cause the core to deform, and as the number of cycles increases, the lithium ion battery changes. The shape will also be aggravated and the capacity will be attenuated.
  • polyolefin films such as commercially available polyethylene films or polypropylene films have poor thermal stability, which causes safety hazards in lithium ion batteries. This is because one of the safety measures for lithium-ion batteries is to interrupt the current, that is, when the internal temperature of the lithium-ion battery is high, the polymer membrane having a porous structure should be able to generate a melting to automatically close the porous structure, thereby rapidly increasing the impedance. Current interruption.
  • the thermal stability of polyolefin film is poor.
  • the self-closing temperature of polyethylene film is 135 ⁇ 140 °C
  • the self-closing temperature of polypropylene film is about 170 °C
  • a large volume shrinkage is easy to cause the diaphragm area to shrink. Small and easily destroyed, causing a short circuit in the lithium-ion battery, causing the battery to explode or catch fire.
  • the separator with the electrode sheet, such as the inorganic oxide CN101246958A, which is directly coated on the carbon negative electrode sheet of the lithium battery to form a composite electrode sheet having a microporous coated separator, and then wound with the positive electrode sheet.
  • the composite electrode sheet prepared by the preparation method contains a hydrophilic polymer, which results in the composite electrode sheet being extremely easy to absorb water, and the added inorganic oxide has a high specific surface area and a strong surface adsorption capacity, and also results in a composite electrode.
  • the first aspect of the embodiments of the present invention provides a composite negative electrode sheet for a lithium ion battery, which is used to solve the internal short circuit and the core deformation of the battery which are easily caused by the winding arrangement of the diaphragm and the positive and negative pole pieces in the prior art.
  • the problem and can improve the safety performance and cycle life of lithium-ion batteries.
  • the second aspect provides a method for preparing the composite negative electrode sheet for a lithium ion battery.
  • a third aspect of the present invention provides a lithium ion battery comprising the composite negative electrode sheet for a lithium ion battery.
  • an embodiment of the present invention provides a composite negative electrode sheet for a lithium ion battery, wherein the composite negative electrode sheet for a lithium ion battery is composed of a negative electrode sheet and a separator composited on a surface of the negative electrode sheet, and the negative electrode sheet is assembled.
  • the fluid is composed of a negative active material coated on a surface of the current collector, and the separator is a polyimide nanofiber membrane.
  • the polyimide nanofiber film has a thickness of 5 ⁇ m to 30 ⁇ m.
  • the polyimide nanofiber membrane has a porosity of 5% to 80% and a pore diameter of ⁇ . ⁇ ⁇ ⁇ ! ⁇ 10 ⁇ m.
  • the current collector is a copper foil or an aluminum foil.
  • the negative electrode active material is any organic compound or inorganic material capable of deintercalating lithium ions.
  • the first aspect of the embodiment of the present invention overcomes the problems of the internal short circuit and the deformation of the battery caused by the winding arrangement of the separator and the positive and negative pole pieces in the prior art.
  • the separator is a porous polymer material polyimide nanofiber.
  • the film which has good heat resistance and can improve the safety performance and cycle life of the lithium ion battery, is suitable for high capacity and power batteries.
  • an embodiment of the present invention provides a method for preparing a composite negative electrode sheet for a lithium ion battery, comprising the steps of: spraying a polyamic acid solution on the surface of the negative electrode sheet by electrospinning, and then performing mechanical rolling, Finally, the thermal imidization treatment converts the polyamic acid sprayed on the surface of the negative electrode sheet into polyimide, and forms a polyimide nanofiber film on the surface of the negative electrode sheet to obtain a composite negative electrode sheet for a lithium ion battery.
  • the polyamic acid solution is prepared as follows: a dibasic organic acid anhydride and an organic diamine are added to an organic solvent, stirred, and a condensation reaction is carried out to obtain a polyamic acid solution.
  • the dibasic organic acid anhydride is pyromellitic acid dianhydride (PMDA), biphenyltetracarboxylic dianhydride (S-BPDA), isopropyl diphthalic anhydride (IPDA), oxybiphenyl tetraphthalic acid dianhydride ( One or more of ODPA), benzophenonetetracarboxylic dianhydride (BTDA) and bisphenol A diether dianhydride (BPADA).
  • the organic diamine is 4,4-diaminodiphenyl ether (4,4-ODA), 3,4-diaminodiphenyl ether (3,4-ODA), m-phenylenediamine (MDA), One or more of p-phenylenediamine (PDA), 3,3-diphenylsulfone diamine (3,3-SDA), biphenyldiamine (BPDA), and isopropyldiphenylamine (IPDA).
  • 4,4-ODA 4,4-diaminodiphenyl ether
  • 3,4-ODA 3,4-diaminodiphenyl ether
  • MDA m-phenylenediamine
  • PDA p-phenylenediamine
  • BPDA biphenyldiamine
  • IPDA isopropyldiphenylamine
  • the organic solvent is hydrazine, hydrazine-dimercaptocarboxamide (DMF), hydrazine, hydrazine-dimercaptoacetamide (DMAc), N-2-mercaptopyrrolidone (NMP), tetrahydrofuran (THF) and hydrazine One or several of the alcohols.
  • the molar ratio of the dibasic organic acid anhydride to the organic diamine is 0.7 to 1.1:1, and the organic solvent is added in an amount of 5 to 8 times the total mass of the dibasic organic acid anhydride and the organic diamine.
  • the temperature of the stirring process is from 0 ° C to 30 ° C, and the stirring time is from 2 to 10 hours.
  • the electrospun spinning needle has a diameter of 0.2 mm to 1.5 mm, a voltage of 100 v to 20 kV, and a distance between the needle and the receiving electrode of 10 cm to 35 cm, and a spinning flow rate. 0.2 to 1 ml / hour.
  • the mechanical rolling has a strength of 1 to 15 MPa, a speed of 0.5 to 1 m/min, and a rolling time of 1 to 5 minutes.
  • the thermal imidization treatment is carried out by gradient heating under nitrogen, argon or vacuum, and the gradient heating is: 100 to 200 ° C for 0.5 to 2 hours, 200 to 250 ° C for 0.5 to 2 hours, 250 to 300 °. C is kept for 0.5 ⁇ 1.5 hours.
  • the thickness of the polyimide nanofiber film is 5 ⁇ to 30 ⁇ .
  • the polyimide nanofiber membrane has a porosity of 5% to 80% and a pore diameter of ⁇ . ⁇ ⁇ ! ⁇ 10 ⁇ m.
  • the negative electrode sheet is composed of a current collector and a negative electrode active material coated on the surface of the current collector.
  • the current collector is a copper foil or an aluminum foil.
  • the negative electrode active material is any organic compound or inorganic material capable of deintercalating lithium ions.
  • the composite negative electrode sheet for a lithium ion battery is prepared by directly laminating the separator on the negative electrode sheet, which simplifies the preparation of the positive and negative electrode sheets and the separator separately in the prior art, and then the separator and the positive and negative electrode sheets are required.
  • the winding process is carried out, and at the same time, the problems of internal short circuit and battery core deformation which are easily caused by the separator and the positive and negative pole piece winding arrangements in the prior art are overcome, and the safety performance and cycle life of the lithium ion battery can be improved. It is therefore suitable for high capacity and power batteries.
  • an embodiment of the present invention provides a lithium ion battery, which is composed of a composite negative electrode sheet for a lithium ion battery, a positive electrode sheet, a nonaqueous electrolyte, and an outer casing, wherein the composite negative electrode sheet for the lithium ion battery is composed of a negative electrode sheet and a composite A separator composed of a separator on a surface of the negative electrode sheet, the negative electrode sheet being composed of a current collector and an anode active material coated on a surface of a current collector, the separator being a polyimide nanofiber membrane.
  • the polyimide nanofiber membrane has a thickness of 5 ⁇ to 30 ⁇ .
  • the polyimide nanofiber membrane has a porosity of 5% to 80% and a pore diameter of ⁇ . ⁇ ⁇ ⁇ ! ⁇ 10 ⁇ m.
  • the current collector is a copper foil or an aluminum foil.
  • the negative electrode active material is any organic compound or inorganic material capable of deintercalating lithium ions.
  • the positive electrode sheet is composed of a current collector and a positive electrode active material coated on the surface of the current collector, and the positive electrode active material is an organic compound or an inorganic material which can deintercalate lithium ions.
  • the non-aqueous electrolyte is an electrolyte of a carbonate solvent, and the electrolyte contains a lithium salt selected from the group consisting of ethylene carbonate (EC), propylene carbonate (PC), and dinonyl carbonate ( One or more of DMC) and cesium carbonate (EMC) selected from the group consisting of LiPF 6 , LiBF 4 , LiSbF 6 , LiC10 4 , LiCF 3 S0 3 , LiA10 4 , LiAlCl 4 , Li ( CF ) 3 S0 2 ) 2 One or more of N, LiBOB and LiDFOB.
  • the outer casing is an aluminum plastic film, a steel shell, an aluminum shell or a plastic shell.
  • the composite negative electrode sheet for a lithium ion battery since the composite negative electrode sheet for a lithium ion battery has been compounded with a separator, it is not necessary to separately provide a separator, and the separator and the positive and negative electrode sheets are not separately wound, and the separator is a porous polymer material.
  • the imide nanofiber membrane has good heat resistance and can improve the safety performance and cycle life of the lithium ion battery. Therefore, the lithium ion battery provided by the third aspect of the embodiment of the invention is easy to prepare, and has excellent safety performance and long The service life can be used as a high capacity and power battery.
  • Fig. 1 is a flow chart showing a method of preparing a composite negative electrode sheet for a lithium ion battery according to an embodiment of the present invention.
  • the following is a preferred embodiment of the embodiments of the present invention. It should be noted that those skilled in the art can make some improvements and refinements without departing from the principles of the embodiments of the present invention. These improvements and retouchings are also considered to be the scope of protection of the embodiments of the present invention.
  • the first aspect of the embodiments of the present invention provides a composite negative electrode sheet for a lithium ion battery, which solves the problems of internal short circuit and battery core deformation caused by the separator and the positive and negative pole piece winding arrangements in the prior art, and Improves the safety and cycle life of lithium-ion batteries.
  • a second aspect of the present invention provides a method for preparing the composite negative electrode sheet for a lithium ion battery.
  • a third aspect of the present invention provides a lithium ion battery comprising the composite negative electrode sheet for a lithium ion battery.
  • an embodiment of the present invention provides a composite negative electrode sheet for a lithium ion battery, wherein the composite negative electrode sheet for a lithium ion battery is composed of a negative electrode sheet and a separator composited on a surface of the negative electrode sheet, and the negative electrode sheet
  • the current collector is composed of a current collector and an anode active material coated on the surface of the current collector
  • the separator is a polyimide nanofiber membrane.
  • the polyimide nanofiber film has a thickness of 5 ⁇ to 30 ⁇ .
  • the polyimide nanofiber membrane is thinner and takes up less space inside the battery when used for preparing a lithium ion battery, thereby increasing the capacity density of the lithium ion battery.
  • Porosity relates to the number of holes per unit area, and the size of the pores relates to the ability of ions to shuttle therethrough.
  • the polyimide nanofiber membrane has a porosity of 5% to 80% and a pore diameter of ⁇ . ⁇ ⁇ ⁇ ! ⁇ 10 ⁇ ⁇ . At this time, the ion current can be quickly passed, thereby completing the rapid transfer of lithium ions between the positive and negative pole pieces during electrochemical charging and discharging.
  • the current collector is copper foil or aluminum foil.
  • the negative electrode active material is any organic compound or inorganic material capable of deintercalating lithium ions, such as a carbon material.
  • the first aspect of the embodiment of the present invention overcomes the problems of the internal short circuit and the deformation of the battery caused by the winding arrangement of the separator and the positive and negative pole pieces in the prior art.
  • the separator is a porous polymer material polyimide nanofiber.
  • the film which has good heat resistance and can improve the safety performance and cycle life of the lithium ion battery, is suitable for high capacity and power batteries.
  • an embodiment of the present invention provides a method for preparing a composite negative electrode sheet for a lithium ion battery.
  • the method includes the following steps: spraying a polyamic acid solution on the surface of the negative electrode sheet by electrospinning. Then, mechanical rolling is performed, and finally, the thermal imidization treatment converts the polyamic acid sprayed on the surface of the negative electrode sheet into polyimide, and forms a polyimide nanofiber film on the surface of the negative electrode sheet to obtain a composite negative electrode sheet for a lithium ion battery.
  • the polyamic acid solution is prepared by adding a dibasic organic acid anhydride and an organic diamine to an organic solvent, stirring, and a condensation reaction to obtain a polyamic acid solution.
  • the dibasic organic acid anhydride is benzoic acid succinic anhydride (PMDA), biphenyltetracarboxylic dianhydride (S-BPDA), and One or more of propyl diphenyl anhydride (IPDA ), oxydiphenyltetradecanoic acid (ODPA), benzophenone tetraacid dianhydride (BTDA), and bisphenol A diether dianhydride (BPADA).
  • PMDA benzoic acid succinic anhydride
  • S-BPDA biphenyltetracarboxylic dianhydride
  • IPDA propyl diphenyl anhydride
  • ODPA oxydiphenyltetradecanoic acid
  • BTDA benzophenone tetraacid dianhydride
  • BPADA bisphenol A diether dianhydride
  • the organic diamine is 4,4-diaminodiphenyl ether (4,4-ODA), 3,4-diaminodiphenyl ether (3,4-00%), m-phenylenediamine (MDA), p-phenylene
  • 4,4-ODA 4,4-diaminodiphenyl ether
  • MDA 3,4-diaminodiphenyl ether
  • MDA m-phenylenediamine
  • PDA 4,4-diaminodiphenyl ether
  • PDA 4,4-diaminodiphenyl ether
  • 3,4-00% 3,4-diaminodiphenyl ether
  • MDA m-phenylenediamine
  • MDA m-phenylenediamine
  • PDA 4,4-diaminodiphenyl ether
  • PDA 4,4-diaminodiphenyl ether
  • BPDA 4,4-diaminodiphenyl ether
  • the organic solvent is one of hydrazine, hydrazine-dimercaptocarboxamide (DMF), hydrazine, hydrazine-dimercaptoacetamide (DMAc), N-2-mercaptopyrrolidone (NMP), tetrahydrofuran (THF) and decyl alcohol.
  • DMF hydrazine-dimercaptocarboxamide
  • DMAc hydrazine
  • DMAc hydrazine-dimercaptoacetamide
  • NMP N-2-mercaptopyrrolidone
  • THF tetrahydrofuran
  • decyl alcohol decyl alcohol
  • the molar ratio of the dibasic organic acid anhydride to the organic diamine is 0.7 to 1.1:1, and the organic solvent is added in an amount of 5 to 8 times the total mass of the dibasic organic acid anhydride and the organic diamine.
  • the temperature of the stirring process is 0 ° C to 30 ° C, and the stirring time is 2 to 10 hours.
  • the spinning needle of the electrospinning has a diameter of 0.2 mm to 1.5 mm, a voltage of 100 v to 20 kV, a distance between the needle and the receiving electrode of 10 cm to 35 cm, and a spinning flow rate of 0.2 to 1 ML/hr.
  • the mechanical rolling strength is 1 to 15 MPa, the speed is 0.5 to 1 m / min, and the rolling time is 1 to 5 minutes.
  • the thermal imidization treatment is carried out by gradient heating under nitrogen, argon or vacuum.
  • the gradient temperature is: 100 ⁇ 200 °C for 0.5 ⁇ 2 hours, 200 ⁇ 250 °C for 0.5 ⁇ 2 hours, 250 ⁇ 300 °C for 0.5. ⁇ 1.5 hours.
  • the polyimide nanofiber membrane has a thickness of 5 ⁇ m to 30 ⁇ m.
  • the polyimide nanofiber membrane has a porosity of 5% to 80% and a pore diameter of 0.01 ⁇ ⁇ ! ⁇ 10 ⁇ ⁇ .
  • the negative electrode sheet is composed of a current collector and a negative electrode active material coated on the surface of the current collector.
  • the current collector is copper foil or aluminum foil.
  • the negative electrode active material is any organic compound or inorganic material capable of deintercalating lithium ions.
  • the separator is directly composited on the negative electrode sheet to prepare a composite for a lithium ion battery.
  • the negative electrode sheet simplifies the prior art process of separately preparing the positive and negative electrode sheets and the separator and then needs to wind the separator and the positive and negative electrode sheets, while overcoming the prior art diaphragm and positive and negative pole coils. It is easy to solve the problem of internal short circuit of the battery and deformation of the battery core, and can improve the safety performance and cycle life of the lithium ion battery, and thus is suitable for high capacity and power batteries.
  • an embodiment of the present invention provides a lithium ion battery, which is composed of a composite negative electrode sheet for a lithium ion battery, a positive electrode sheet, a nonaqueous electrolyte, and an outer casing, wherein the composite negative electrode sheet for the lithium ion battery is composed of a negative electrode sheet and a composite A separator composed of a separator on a surface of the negative electrode sheet, the negative electrode sheet being composed of a current collector and an anode active material coated on a surface of a current collector, the separator being a polyimide nanofiber membrane.
  • the polyimide nanofiber membrane has a thickness of 5 ⁇ m to 30 ⁇ m.
  • the polyimide nanofiber membrane has a porosity of 5% to 80% and a pore diameter of 0.01 ⁇ ⁇ ! ⁇ 10 ⁇ ⁇ .
  • the current collector is copper foil or aluminum foil.
  • the negative electrode active material is any organic compound or inorganic material capable of deintercalating lithium ions.
  • the positive electrode sheet is composed of a current collector and a positive electrode active material coated on the surface of the current collector, and the positive electrode active material is an organic compound or an inorganic material which can deintercalate lithium ions.
  • the nonaqueous electrolyte is an electrolyte of a carbonate solvent containing a lithium salt selected from the group consisting of ethylene carbonate (EC), propylene carbonate (PC), dinonyl carbonate (DMC), and One or more of ethyl lanthanum carbonate (EMC) selected from the group consisting of LiPF 6 , LiBF 4 , LiSbF 6 , LiC10 4 , LiCF 3 S0 3 , LiA10 4 , LiAlCl 4 , Li ( CF 3 S0 2 One or more of 2 N, LiBOB and LiDFOB.
  • a lithium salt selected from the group consisting of ethylene carbonate (EC), propylene carbonate (PC), dinonyl carbonate (DMC), and One or more of ethyl lanthanum carbonate (EMC) selected from the group consisting of LiPF 6 , LiBF 4 , LiSbF 6 , LiC10 4 , LiCF 3 S0 3 , LiA10 4
  • the outer casing is an aluminum plastic film, a steel shell, an aluminum shell or a plastic shell.
  • the composite negative electrode sheet and the positive electrode sheet for the lithium ion battery are cut to a certain size, and then the composite negative electrode sheet and the positive electrode sheet for the lithium ion battery are wound and pre-sealed with an aluminum plastic film to obtain a 423485 square type battery core, which is then completed.
  • the square-wound soft-packed battery is finally filled with a non-aqueous electrolyte to produce a lithium-ion battery.
  • the separator is a porous polymer material.
  • the imide nanofiber membrane has good heat resistance and can improve the safety performance and cycle life of the lithium ion battery. Therefore, the lithium ion battery provided by the third aspect of the embodiment of the invention is easy to prepare, and has excellent safety performance and long The service life can be used as a high capacity and power battery.
  • the preparation method of the composite negative electrode sheet for a lithium ion battery comprises the following steps:
  • a mixture of negative active material artificial graphite, 3 g of binder styrene butadiene rubber (SBR) and 3 g of carboxymethylcellulose (CMC) was added to 200 g of water, and then stirred in a vacuum mixer to form a uniform slurry. .
  • the slurry was uniformly coated on both sides of a 9 ⁇ m copper foil, and the coated surface density was controlled to be 17.8 mg/cm 2 , and then dried at 100 ° C, and pressed to obtain a negative electrode sheet having a thickness of 120 ⁇ m.
  • the polyamic acid solution was electrospun onto a prepared negative electrode sheet having a needle diameter of 1.5 mm, a spinning voltage of 20 kV, a needle to negative electrode sheet distance of 18 cm, electrospinning for 1 hour, and then passing through 90 °C oven pre-drying, and then rolling through the roller press, the pressure is 15 MPa, the speed is 0.5 m / Minutes, rolling for 5 minutes, controlling the thickness of the polyamic acid nanofiber film to 30 ⁇ , heating the polyamic acid to polyimide under heating in a nitrogen atmosphere, and maintaining the heating temperature at 200 ° C for 0.5 hour, 250 °
  • the mixture was kept at 0.5 hour for 0.5 hour and at 350 ° C for 0.5 hour to obtain a composite negative electrode sheet for a lithium ion battery having a polyimide nanofiber film.
  • the composite negative electrode sheet for a lithium ion battery prepared in this embodiment is composed of a negative electrode sheet and a separator directly laminated on the surface of the negative electrode sheet, and the negative electrode sheet is composed of a current collector and a negative electrode active material coated on the surface of the current collector, and the separator is a polyacyl group.
  • Imine nanofiber membrane The polyimide nanofiber membrane has a thickness of 30 ⁇ m.
  • the polyimide nanofiber membrane has a porosity of 70% and a pore diameter of 10 ⁇ m.
  • the composite negative electrode sheet for a lithium ion battery obtained in Example 1 was cut to a size of 405 mm ⁇ 80 mm, which contained 5.3 g of active ingredient artificial graphite.
  • the composite negative electrode sheet and the positive electrode sheet for lithium ion battery cut into a certain shape are pre-sealed by aluminum plastic film to obtain a 423485 square type battery core, and then the square-wound soft-pack battery is completed, and finally the non-water is injected.
  • the non-aqueous electrolyte is ethylene carbonate: mercaptoethyl carbonate: a mixed solution of diethyl carbonate in a volume ratio of 1:1:1, containing 1 mol of lithium hexafluorophosphate,
  • a lithium ion battery has a design capacity of 1600 mAh.
  • the preparation method of the composite negative electrode sheet for a lithium ion battery comprises the following steps: (1) Synthesis of polyamic acid solution
  • a mixture of negative active material artificial graphite, 3 g of binder styrene butadiene rubber (SBR) and 3 g of carboxymethylcellulose (CMC) was added to 200 g of water, and then stirred in a vacuum mixer to form a uniform slurry. .
  • the slurry was uniformly coated on both sides of a 9 ⁇ m copper foil, and the coated surface density was controlled to be 17.8 mg/cm 2 , and then dried at 100 ° C, and pressed to obtain a negative electrode sheet having a thickness of 120 ⁇ m.
  • the polyamic acid solution was electrospun onto the prepared negative electrode sheet, the needle diameter was 1 mm, the spinning voltage was 1000 volts, the distance from the needle to the negative electrode sheet was 20 cm, electrospinning was 0.8 hour, and then passed through 90°.
  • the C oven is pre-baked and then rolled by a roller press at a pressure of 5 MPa, a speed of 0.8 m/min, and a rolling pressure of 3 minutes.
  • the polyamic acid nanofiber film is controlled to have a thickness of 15 ⁇ m and heated under an argon atmosphere.
  • the polyamic acid is converted into a polyimide, and the heating temperature is maintained at 150 ° C for 1 hour, at 220 ° C for 1 hour, and at 300 ° C for 1 hour to obtain lithium having a polyimide nanofiber membrane.
  • the composite negative electrode sheet for a lithium ion battery is composed of a negative electrode sheet and a separator directly laminated on the surface of the negative electrode sheet, and the negative electrode sheet is composed of a current collector and a negative electrode active material coated on the surface of the current collector, and the separator is a polyimide nanofiber membrane.
  • the polyimide nanofiber membrane has a thickness of 15 ⁇ m.
  • the polyimide nanofiber membrane has a porosity of 60% and a pore diameter of 1 ⁇ m.
  • the preparation method of the lithium ion battery is the same as that in the first embodiment.
  • Embodiment 3 The preparation method of the composite negative electrode sheet for a lithium ion battery comprises the following steps:
  • a mixture of negative active material artificial graphite, 3 g of binder styrene butadiene rubber (SBR) and 3 g of carboxymethylcellulose (CMC) was added to 200 g of water, and then stirred in a vacuum mixer to form a uniform slurry. .
  • the slurry was uniformly coated on both sides of a 9 ⁇ m copper foil, and the coated surface density was controlled to be 17.8 mg/cm 2 , and then dried at 100 ° C, and pressed to obtain a negative electrode sheet having a thickness of 120 ⁇ m.
  • the polyamic acid solution was electrospun onto the prepared negative electrode sheet, the diameter of the needle was 0.2 mm, the spinning voltage was 100 volts, the distance from the needle to the negative electrode sheet was 25 cm, electrospinning was 0.2 hour, and then passed through 90°.
  • the amic acid is converted into a polyimide, and the heating temperature is maintained at 100 ° C for 2 hours, at 200 ° C for 2 hours, and at 250 ° C for 0.5 hour to obtain a lithium ion battery having a polyimide nanofiber membrane.
  • a composite negative electrode sheet was used.
  • the preparation method of the lithium ion battery is the same as that in the first embodiment.
  • the composite negative electrode sheet for a lithium ion battery is composed of a negative electrode sheet and a separator directly laminated on the surface of the negative electrode sheet, and the negative electrode sheet is composed of a current collector and a negative electrode active material coated on the surface of the current collector, and the separator is a polyimide nanofiber membrane.
  • the polyimide nanofiber membrane has a thickness of 5 ⁇ m.
  • the polyimide nanofiber membrane has a porosity of 50% and a pore diameter of 0.1 ⁇ m. Comparative example one
  • a mixture of negative active material artificial graphite, 3 g of binder styrene butadiene rubber (SBR) and 3 g of carboxymethylcellulose (CMC) was added to 200 g of water, and then stirred in a vacuum mixer to form a uniform slurry. .
  • the slurry was uniformly coated on both sides of a 9 ⁇ m copper foil, and the coated surface density was controlled to be 17.8 mg/cm 2 , and then dried at 100 ° C, and pressed to obtain a negative electrode sheet having a thickness of 120 ⁇ m.
  • the separator is made of commercial polyolefin separator Celgard 2400 (single-layer polypropylene film), and then the separator is wound with the positive and negative pole pieces. After assembly and encapsulation, the liquid is injected, sealed, and finally activated and tested for performance to obtain a lithium ion battery. .
  • the aqueous polymer colloidal emulsion is subjected to stepwise polymerization: 1000 parts of distilled water and 100 parts of polyethylidene pyrrolidone are added to a four-reaction reaction vessel of condensed water, and the reaction vessel is heated to 90 ° C, and stirred to dissolve until the material is transparent.
  • aqueous polymer colloidal emulsion was added to 15 parts of white carbon black and 100 parts of triethyl phosphate plasticizer, and ball-milled for 5 hours to prepare an aqueous polymer slurry.
  • the aqueous polymer slurry is coated on the prepared copper foil negative electrode sheet by a coating device, and the water and the plasticizer are volatilized by a hot air of 100 ° C and an infrared irradiation drying tunnel to obtain a polymer coating.
  • the composite negative electrode sheet and the positive electrode sheet for the lithium ion battery are assembled, packaged, injected, sealed, and finally activated and subjected to performance test to obtain a lithium ion battery.
  • the lithium ion batteries produced in the above examples and comparative examples were experimental batteries for the performance test of the following effect examples.
  • the test method is as follows: The lithium ion battery is charged to a 100% state of charge with a current of 1 C (1.6 A), and then charged to a constant voltage of 10 V for 2 hours with a current of 3 C (4.8 A) to observe whether the lithium ion battery is ignited or exploded.
  • the test method is as follows: The lithium ion battery is charged to a 100% state of charge with a current of 1 C (1.6 A), placed in an oven, and the oven temperature is raised from room temperature to 150 ° C at 5 ° C for 10 minutes without short circuit. In the case, continue to increase to 5 ° C to 180 ° C for 10 minutes, observe whether the lithium-ion battery is short-circuited. The lithium ion battery voltage drop greater than 0.2 volts is considered a short circuit.
  • the test method is as follows: Lithium-ion battery is charged to 100% charge state with 1C (1.6A) current, and a 2.7 mm diameter iron round nail penetrates the lithium ion battery body at a speed of 5 mm/sec, and the lithium ion is monitored. The temperature of the battery surface and whether it is a fire or explosion.
  • the test method is as follows: 1C (1.6A) current is charged to 4.2 volts, then constant voltage to current less than 80 mA, 1C (1.6A) current is discharged to 3.0 volts, thus repeating charge and discharge, and obtaining the 500th discharge capacity and initial The ratio of the initial discharge capacity.
  • the lithium ion battery prepared by using the composite negative electrode sheet for lithium ion battery of the embodiment of the invention has higher heat resistance, better safety performance and more safety than the lithium ion battery prepared by the comparative example. Good cycle performance.
  • the results are analyzed as follows:
  • the composite negative electrode sheet for a lithium ion battery is compounded with a polyimide nanofiber membrane, which can withstand high temperature thermal shock, and does not cause thermal runaway under internal partial short circuit conditions, and a composite negative electrode for a lithium ion battery.
  • the sheet does not generate tensile stress during the winding assembly process, and the internal resistance is not increased due to the deformation of the battery core during the cycle, so the cycle performance is better.

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  • Electrochemistry (AREA)
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Abstract

L'invention concerne une feuille d'électrode négative composite pour une batterie au lithium-ion et un procédé de préparation de celle-ci et une batterie au lithium-ion. Le procédé de préparation pour une feuille d'électrode négative composite pour une batterie au lithium-ion comprend les étapes de : revêtement par pulvérisation d'une solution d'acide polyamique sur la surface d'une feuille d'électrode négative par filage électrostatique, puis réalisation d'un enroulement mécanique, et enfin conversion de l'acide polyamique revêtu par pulvérisation sur la surface de la feuille d'électrode négative en polyimide par traitement d'imidisation thermique pour former un film en nanofibres de polyimide sur la surface de la feuille d'électrode négative, de façon à obtenir une feuille d'électrode négative composite pour une batterie au lithium-ion. Le procédé de préparation selon la présente invention simplifie le processus dans l'état antérieur de la technique qui nécessite une préparation séparée d'une feuille d'électrode positive et négative et d'un séparateur suivi par un enroulement du séparateur avec la feuille d'électrode positive et négative, et en même temps, résout les problèmes de court-circuit interne de batterie et de déformation facilement provoqués par un agencement enroulé du séparateur et de la feuille d'électrode positive et négative dans l'état antérieur de la technique. La batterie au lithium-ion fabriquée avec la feuille d'électrode négative composite pour une batterie au lithium-ion selon la présente invention possède une excellente performance de sécurité et une longue durée de vie en service, et peut être utilisée en tant que batteries à énergie et capacité élevées.
PCT/CN2013/073487 2012-09-24 2013-03-29 Feuille d'électrode négative composite pour batterie au lithium-ion et son procédé de préparation et batterie au lithium-ion WO2014044040A1 (fr)

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