WO2018036309A1 - 正极添加剂及其制备方法、正极片及锂离子二次电池 - Google Patents

正极添加剂及其制备方法、正极片及锂离子二次电池 Download PDF

Info

Publication number
WO2018036309A1
WO2018036309A1 PCT/CN2017/093546 CN2017093546W WO2018036309A1 WO 2018036309 A1 WO2018036309 A1 WO 2018036309A1 CN 2017093546 W CN2017093546 W CN 2017093546W WO 2018036309 A1 WO2018036309 A1 WO 2018036309A1
Authority
WO
WIPO (PCT)
Prior art keywords
positive electrode
lithium
lithium carbonate
lithium ion
electrode additive
Prior art date
Application number
PCT/CN2017/093546
Other languages
English (en)
French (fr)
Inventor
洪响
姜玲燕
Original Assignee
宁德时代新能源科技股份有限公司
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 宁德时代新能源科技股份有限公司 filed Critical 宁德时代新能源科技股份有限公司
Priority to EP17842732.4A priority Critical patent/EP3480878A4/en
Publication of WO2018036309A1 publication Critical patent/WO2018036309A1/zh
Priority to US16/267,009 priority patent/US10840501B2/en

Links

Classifications

    • 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
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • 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
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01D—COMPOUNDS OF ALKALI METALS, i.e. LITHIUM, SODIUM, POTASSIUM, RUBIDIUM, CAESIUM, OR FRANCIUM
    • C01D15/00—Lithium compounds
    • C01D15/08—Carbonates; Bicarbonates
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G51/00—Compounds of cobalt
    • C01G51/06—Carbonates
    • 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
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/131—Electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
    • 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
    • H01M4/136—Electrodes based on inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy
    • 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
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/362—Composites
    • H01M4/366—Composites as layered products
    • 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
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • H01M4/583—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
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
    • H01M2004/028—Positive electrodes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2220/00—Batteries for particular applications
    • H01M2220/20—Batteries in motive systems, e.g. vehicle, ship, plane
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2220/00—Batteries for particular applications
    • H01M2220/30—Batteries in portable systems, e.g. mobile phone, laptop
    • 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 invention relates to the technical field of batteries, in particular to a positive electrode additive and a preparation method thereof, a positive electrode sheet and a lithium ion secondary battery.
  • Lithium-ion secondary batteries have the advantages of high operating voltage, high specific energy, high number of cycles, long storage time, etc., and are widely used not only in portable electronic devices such as mobile phones, digital cameras and laptops, but also in electrics. Automobiles, electric bicycles and other vehicles are also widely used, among which electric vehicles have more stringent requirements for the safety performance of lithium ion secondary batteries.
  • a lithium ion secondary battery used as an electric vehicle driving power source generally has a pressure detecting type current blocking device in addition to a safety valve for explosion prevention.
  • the current blocking device is activated when the lithium ion secondary battery has an abnormal internal rapid gas production, and the lithium ion secondary battery is prevented from being out of control by blocking the current, thereby avoiding a safety accident.
  • lithium carbonate is usually added as a supercharged gas additive in the positive electrode sheet.
  • Lithium carbonate decomposes when the working voltage of the lithium ion secondary battery reaches a certain level, and carbon dioxide is generated to activate the current blocking device to ensure the safety of the lithium ion secondary battery.
  • the initial degradation voltage of lithium carbonate is too high (> 4.8V)
  • thermal runaway of some high-energy lithium-ion secondary batteries before the voltage is reached has begun to occur, and the current blocking device cannot be made to function properly.
  • Increasing the lithium carbonate content in the positive electrode sheet can improve its voltage sensitivity to some extent, however, this will significantly lower the content of the active material in the positive electrode sheet and the energy density of the lithium ion secondary battery as a whole.
  • an object of the present invention is to provide a positive electrode additive, a preparation method thereof, a positive electrode sheet and a lithium ion secondary battery, which can be used without affecting the electrical properties of the lithium ion secondary battery.
  • the safety performance of the lithium ion secondary battery is greatly improved.
  • the present invention provides a positive electrode additive comprising a modified lithium carbonate.
  • the modified lithium carbonate includes lithium carbonate particles and a polymer coating layer.
  • the polymer coating layer coats the surface of the lithium carbonate particles and includes a polymer.
  • the invention provides a method for preparing a positive electrode additive for preparing the positive electrode additive of the first aspect of the invention, comprising the steps of: (1) dispersing lithium carbonate particles in a polymer organic The suspension is prepared in a solvent solution; (2) the suspension is treated by spray drying to obtain a positive electrode additive.
  • a positive electrode sheet comprising a positive electrode current collector and a positive electrode film.
  • the positive electrode film is disposed on the positive electrode current collector and includes a positive electrode active material.
  • the positive electrode film further comprises the positive electrode additive of the first aspect of the invention.
  • the invention provides a lithium ion secondary battery comprising the positive electrode sheet of the third aspect of the invention.
  • the positive electrode additive of the invention has low cost and simple preparation method, and can be used in a lithium ion secondary battery to greatly improve the safety performance of the lithium ion secondary battery without affecting the electrical performance of the lithium ion secondary battery.
  • the positive electrode additive and the preparation method thereof, the positive electrode sheet and the lithium ion secondary battery according to the present invention are explained in detail below.
  • the positive electrode additive according to the first aspect of the invention includes a modified lithium carbonate.
  • the modified lithium carbonate includes lithium carbonate particles and a polymer coating layer.
  • the polymer coating layer coats the surface of the lithium carbonate particles and includes a polymer.
  • the polymer coating layer controls the electronic resistance and ionic resistance of the lithium carbonate particles and the pole piece by performing polymer surface coating modification on the common lithium carbonate particles to make carbonic acid
  • the local voltage of the peripheral region of the lithium particles is higher than the overall voltage of the pole piece.
  • the lithium carbonate particles have an average particle diameter (i.e., D50) of from 20 nm to 20 ⁇ m.
  • the excessively small average particle diameter of the lithium carbonate particles is disadvantageous for the dispersion of the lithium carbonate particles in the positive electrode slurry, and the excessive average particle diameter of the lithium carbonate particles may affect the electron conduction and ion conduction of the positive electrode sheet, thereby affecting lithium.
  • the lithium carbonate particles have a particle diameter of 100 nm to 5 ⁇ m.
  • the polymer may be selected from the group consisting of vinylidene fluoride-hexafluoropropylene copolymer (PVDF-HFP), polyvinylidene fluoride (PVDF), and polyacrylonitrile (PAN). , polymethyl methacrylate (PMMA), polyacrylic acid (PAA), polyethylene oxide (PEO), polyethylene (PE), polypropylene (PP), polytetrafluoroethylene (PTFE), ethylene-propylene- One or more of butadiene terpolymers (EDPM).
  • PVDF-HFP vinylidene fluoride-hexafluoropropylene copolymer
  • PVDF polyvinylidene fluoride
  • PAN polyacrylonitrile
  • PMMA polymethyl methacrylate
  • PAA polyacrylic acid
  • PEO polyethylene oxide
  • PE polyethylene
  • PP polypropylene
  • PTFE polytetrafluoroethylene
  • EDPM ethylene-propylene- One
  • the polymer has a weight average molecular weight of from 50,000 to 500,000.
  • the polymer has a weight average molecular weight of from 100,000 to 250,000.
  • the mass of the polymer coating layer is from 1% to 50% by mass of the lithium carbonate particles.
  • the method for preparing a positive electrode additive according to the second aspect of the present invention for preparing the positive electrode additive according to the first aspect of the present invention, comprising the steps of: (1) dispersing lithium carbonate particles in an organic solvent solution of a polymer to prepare a suspension; (2) The suspension was treated by a spray drying method to obtain a positive electrode additive.
  • the organic solvent may be selected from the group consisting of ethers, esters, nitriles, amides, alcohols, and halogenated alkanes. Or several. Specifically, the ether may be selected from one or two of diethyl ether and tetrahydrofuran (THF); the ester may be selected from one of ethyl acetate, methyl formate, and dimethyl phthalate.
  • the positive electrode sheet according to the third aspect of the invention includes a positive electrode current collector and a positive electrode film.
  • the positive electrode film is disposed on a positive electrode current collector and includes a positive electrode active material.
  • the positive electrode film further includes the positive electrode additive according to the first aspect of the invention.
  • the positive electrode film further includes a conductive agent.
  • the conductive agent may be selected from one or more of graphite, acetylene black, conductive carbon black, superconducting carbon black, graphene, carbon nanotubes, conductive fibers, metal powder, and organic conductive polymer.
  • the graphite may be selected from natural graphite or artificial graphite.
  • the acetylene black may be selected from ketjen black.
  • the electrically conductive fibers may be selected from carbon fibers or metal fibers.
  • the metal powder may be selected from copper powder or nickel powder.
  • the organic conductive polymer may be selected from polyphenylene derivatives.
  • the positive electrode film further includes a binder.
  • the binder may be selected from one or more of polyvinylidene fluoride, polyvinyl alcohol, polyurethane, polyacrylate, butyl rubber, epoxy resin, vinyl acetate resin, and chlorinated rubber.
  • the positive electrode active material may be selected from a lithium metal oxide having a layer structure, a metal oxide containing no lithium, a lithium metal oxide having a spinel structure, and lithium.
  • a lithium metal oxide having a layer structure a metal oxide containing no lithium
  • a lithium metal oxide having a spinel structure a lithium metal oxide having a spinel structure
  • lithium One or more of metal phosphate, lithium metal fluoride sulfate, lithium metal vanadate.
  • the lithium metal oxide of the layered structure may be selected from lithium cobaltate (LCO), nickel cobalt manganese ternary material (NCM), nickel cobalt aluminum ternary material (NCA).
  • the lithium-free metal oxide may be selected from V 2 O 5 or MnO 2 .
  • the lithium metal oxide of the spinel structure may be selected from lithium manganate (LiMn 2 O 4 ).
  • the lithium metal phosphate may be selected from lithium iron phosphate (LFP).
  • the lithium metal fluoride sulfate may be selected from lithium cobalt fluoride sulfate (LiCoFSO 4 ).
  • the lithium metal vanadate may be selected from lithium nickel vanadate (LiNiVO 4 ).
  • the cathode current collector may be selected from the group consisting of stainless steel, nickel, titanium, carbon, aluminum, a conductive resin, a copper sheet coated with nickel or titanium, coated with nickel or titanium. One or several of the stainless steel sheets.
  • the mass of the positive electrode additive is 0.5% to 10% by mass of the positive electrode active material.
  • the excessively high quality of the positive electrode additive lowers the energy density of the positive electrode sheet, affects the power performance of the lithium ion secondary battery, and increases the gas production amount in the normal use of the lithium ion secondary battery. If the quality of the positive electrode additive is too low, the current blocking device cannot cut off the charging circuit in time when the lithium ion secondary battery is overcharged, and the thermal runaway of the lithium ion secondary battery cannot be effectively controlled.
  • the mass of the positive electrode additive is the mass of the positive electrode active material 1% to 5%.
  • a lithium ion secondary battery according to a fourth aspect of the present invention which comprises the positive electrode sheet of the third aspect of the invention, is explained.
  • a lithium ion secondary battery according to a fourth aspect of the present invention further includes a negative electrode sheet, a separator, and an electrolyte.
  • the separator is spaced between the positive and negative sheets.
  • the negative electrode sheet includes a negative electrode active material.
  • the negative active material may be selected from the group consisting of artificial graphite, natural graphite, Si elemental substance, Sn elemental substance, SiO x (0 ⁇ x ⁇ 2), SnO y (0 ⁇ y ⁇ 2), Si alloy (ie, Si and Ti, Fe, One of alloy materials formed by one or more of Co, Ni, and Cu), or one of Sn alloys (ie, alloy materials formed of one or more of Sn, Ti, Co, Ni, and Cu) or Several.
  • the electrolyte solution includes a non-aqueous organic solvent and an electrolyte dissolved therein.
  • the non-aqueous organic solvent may be selected from one or more of ethylene carbonate, propylene carbonate, dimethyl carbonate, diethyl carbonate, ethyl methyl carbonate, and vinylidene carbonate.
  • the electrolyte may be selected from one of LiPF 6 , LiBF 4 , LiCl, LiAlCl 4 , LiSbF 6 , LiSCN, LiCF 3 SO 3 , LiCF 3 CO 2 , LiN(CF 3 SO 2 ), LiAsF 6 , LiBC 4 O 8 Kind or several.
  • the specific kind of the separator is not particularly limited, and may be any separator material used in the conventional lithium ion secondary battery.
  • the separator is selected from the group consisting of polyethylene, polypropylene, polyvinylidene fluoride, and multilayer composite films thereof.
  • the binder PVDF is dissolved in N-methylpyrrolidone, and then a positive electrode active material NCM (111), a positive electrode additive, and a conductive agent acetylene black are added thereto, and fully mixed to obtain a positive electrode slurry, wherein PVDF and NCM (111) are obtained.
  • the mass ratio of the positive electrode additive and acetylene black is 3:100:10:2.
  • the positive electrode slurry was coated on both sides of a 12 ⁇ m thick positive electrode current collector aluminum foil, and then air-dried at 85 ° C for 20 hours, and cold rolled up to obtain a positive electrode sheet.
  • the negative active material artificial graphite, conductive agent acetylene black, binder styrene-butadiene rubber emulsion (SBR), thickener sodium carboxymethyl cellulose (CMC) are dissolved in solvent deionized according to mass ratio of 97:1:1.5:0.5.
  • the negative electrode slurry was prepared in water, and then coated on the front and back sides of the negative electrode current collector copper foil, and then air-dried at 110 ° C for 20 hours, and cold rolled up to obtain a negative electrode sheet.
  • ethylene carbonate, diethyl carbonate, ethyl methyl carbonate, and vinylidene carbonate were mixed at a mass ratio of 8:85:5:2 to obtain
  • the non-aqueous organic solvent is mixed, and the sufficiently dried lithium salt LiPF 6 is dissolved in the above mixed non-aqueous organic solvent, and after stirring uniformly, an electrolytic solution is obtained, wherein the mass ratio of LiPF 6 to the mixed non-aqueous organic solvent is 8:92.
  • the positive electrode sheet, the separator (PE film) and the negative electrode sheet are stacked in order, so that the separator is in a role of isolation between the positive and negative electrodes, and then wound to obtain a bare cell; the bare cell is placed in an outer package In the foil, the prepared electrolyte solution is injected into the dried battery cell, and then subjected to vacuum encapsulation, standing, formation, shaping, and the like to obtain a lithium ion secondary battery.
  • a lithium ion secondary battery was prepared in accordance with the method of Example 1, except that:
  • the suspension is treated by a spray drying method to obtain lithium carbonate particles coated with a polymer coating layer, thereby obtaining a positive electrode additive modified lithium carbonate, wherein the polymer coating layer
  • the mass is 10% of the mass of the lithium carbonate particles.
  • the binder PVDF is dissolved in N-methylpyrrolidone, and then a positive electrode active material NCM (523), a positive electrode additive, and a conductive agent acetylene black are added thereto, and fully mixed to obtain a positive electrode slurry, wherein PVDF and NCM (523) are obtained.
  • the mass ratio of the positive electrode additive and acetylene black is 3:100:1:2.
  • the positive electrode slurry was coated on both sides of a 12 ⁇ m thick positive electrode current collector aluminum foil, and then air-dried at 85 ° C for 20 hours, and cold rolled up to obtain a positive electrode sheet.
  • a lithium ion secondary battery was prepared in accordance with the method of Example 1, except that:
  • the suspension was treated by a spray drying method to obtain lithium carbonate particles coated with a polymer coating layer to obtain a positive electrode additive-modified lithium carbonate, wherein the mass of the polymer coating layer was 1% by mass of the lithium carbonate particles.
  • the binder PVDF is dissolved in N-methylpyrrolidone, and then a positive electrode active material NCM (622), a positive electrode additive, and a conductive agent acetylene black are added thereto, and fully mixed to obtain a positive electrode slurry, wherein PVDF and NCM (622) are obtained.
  • the mass ratio of the positive electrode additive and acetylene black is 3:100:0.5:2.
  • the positive electrode slurry was coated on both sides of a 12 ⁇ m thick positive electrode current collector aluminum foil, and then air-dried at 85 ° C for 20 hours, and cold rolled up to obtain a positive electrode sheet.
  • a lithium ion secondary battery was prepared in accordance with the method of Example 1, except that:
  • the binder PVDF is dissolved in N-methylpyrrolidone, and then a positive electrode active material lithium cobaltate, a positive electrode additive, and a conductive agent acetylene black are added thereto, and fully mixed to obtain a positive electrode slurry, wherein PVDF, lithium cobaltate, and a positive electrode are obtained.
  • the mass ratio of the additive to acetylene black is 3:100:5:2.
  • the positive electrode slurry was coated on both sides of a 12 ⁇ m thick positive electrode current collector aluminum foil, and then air-dried at 85 ° C for 20 hours, and cold rolled up to obtain a positive electrode sheet.
  • a lithium ion secondary battery was prepared in accordance with the method of Example 1, except that:
  • the binder PVDF is dissolved in N-methylpyrrolidone, and then the positive electrode active material NCA, the positive electrode additive, and the conductive agent acetylene black are added thereto, and fully mixed to obtain a positive electrode slurry, wherein PVDF, NCA, positive electrode additive, and acetylene black are obtained.
  • the mass ratio is 3:100:3:2.
  • the positive electrode slurry was coated on both sides of a 12 ⁇ m thick positive electrode current collector aluminum foil, and then air-dried at 85 ° C for 20 hours, and cold rolled up to obtain a positive electrode sheet.
  • a lithium ion secondary battery was prepared in accordance with the method of Example 1, except that the positive electrode additive was ordinary lithium carbonate (i.e., lithium carbonate having no coating layer).
  • a lithium ion secondary battery was prepared in accordance with the method of Example 2, except that the positive electrode additive was ordinary lithium carbonate (i.e., lithium carbonate having no coating layer).
  • a lithium ion secondary battery was prepared in accordance with the method of Example 3, except that the positive electrode additive was ordinary lithium carbonate (i.e., lithium carbonate having no coating layer).
  • a lithium ion secondary battery was prepared in accordance with the method of Example 4, except that the positive electrode additive was ordinary lithium carbonate (i.e., lithium carbonate having no coating layer).
  • a lithium ion secondary battery was prepared in accordance with the method of Example 5, except that the positive electrode additive was ordinary lithium carbonate (i.e., lithium carbonate having no coating layer).
  • the lithium ion secondary battery was allowed to stand at 25 ° C for 5 min, charged at a constant current of 0.5 C to a voltage of 4.2 V, and then charged at a constant voltage of 4.2 V until the current was 0.05 C, at which time the lithium ion secondary battery reached a full charge state ( 100% SOC), allowed to stand for 5 min, and then discharged at a constant current of 0.1 C and 1 C respectively to a voltage of 3.0 V.
  • Each group was tested with 4 lithium ion secondary batteries and averaged.
  • 1C/0.1C discharge rate performance (%) of lithium ion secondary battery 10th cycle discharge capacity of lithium ion secondary battery at 1C / discharge amount of 10th cycle of lithium ion secondary battery at 0.1C ⁇ 100%.
  • the lithium ion secondary battery was allowed to stand at 25 ° C for 5 min, charged at a constant current of 0.5 C to a voltage of 4.2 V, and then charged at a constant voltage of 4.2 V until the current was 0.05 C, at which time the lithium ion secondary battery reached a full charge state ( 100% SOC), let stand for 5 min, then charge to a voltage of 5 V at a rate of 0.1 C, and then continue charging at a constant voltage of 5 V until the current blocking device of the lithium ion secondary battery functions to obtain lithium at the time of overcharge termination.
  • the voltage of the ion secondary battery ie, the overcharge failure voltage
  • the SOC state ie, the overcharge failure SOC
  • the rate performance of the lithium ion secondary battery of Example 1-5 was not significantly different from the rate performance of the lithium ion secondary battery of Comparative Examples 1-5, which indicates the use of the positive electrode additive of the present invention. There is basically no influence on the electrical properties of the lithium ion secondary battery.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Materials Engineering (AREA)
  • Inorganic Chemistry (AREA)
  • Manufacturing & Machinery (AREA)
  • Organic Chemistry (AREA)
  • Composite Materials (AREA)
  • Battery Electrode And Active Subsutance (AREA)
  • Secondary Cells (AREA)

Abstract

本发明提供一种正极添加剂及其制备方法、正极片及锂离子二次电池。所述正极添加剂包括改性碳酸锂。所述改性碳酸锂包括碳酸锂颗粒以及聚合物包覆层。所述包覆层包覆在所述碳酸锂颗粒的表面且包括聚合物。本发明的正极添加剂成本低廉、制备方法简单，将其添加到正极片并应用在锂离子二次电池中时能在不影响锂离子二次电池的电性能的基础上大幅度提升锂离子二次电池安全性能。

Description

正极添加剂及其制备方法、正极片及锂离子二次电池 技术领域
本发明涉及电池技术领域，尤其涉及一种正极添加剂及其制备方法、正极片及锂离子二次电池。
背景技术
锂离子二次电池具有工作电压高、比能量高、循环使用次数多、存储时间长等优点，不仅在便携式电子设备，例如移动电话、数码摄像头和手提电脑等设备中得到广泛应用，而且在电动汽车、电动自行车等交通工具中也有广泛应用，其中电动交通工具对锂离子二次电池的安全性能有更严苛要求。
用作电动交通工具驱动电源的锂离子二次电池除了具有防爆用的安全阀外，一般还具备压力检测式的电流阻断装置。电流阻断装置在锂离子二次电池发生异常的内部快速产气时启动，通过阻断电流来防止锂离子二次电池热失控，避免导致安全事故。
为使电流阻断装置更灵敏地监控锂离子二次电池的健康状态，提高锂离子二次电池的耐过充性能，现有技术中通常在正极片中添加碳酸锂作为过充产气添加剂，碳酸锂在锂离子二次电池的工作电压达到一定程度时发生分解，产生二氧化碳从而启动电流阻断装置，保证锂离子二次电池的安全性。然而，由于碳酸锂起始降解电压过高(>4.8V)，部分高能量锂离子二次电池在达到此电压前热失控已开始发生，无法使得电流阻断装置发挥应有作用。提高正极片中碳酸锂含量能在一定程度上改善其电压敏感性，然而这将显著降低正极片中活性物质的含量和锂离子二次电池整体的能量密度。
发明内容
鉴于背景技术中存在的问题，本发明的目的在于提供一种正极添加剂及其制备方法、正极片及锂离子二次电池，所述正极添加剂能在不影响锂离子二次电池的电性能的基础上大幅度提升锂离子二次电池的安全性能。
为了达到上述目的，在本发明的第一方面，本发明提供了一种正极添加剂，其包括改性碳酸锂。所述改性碳酸锂包括碳酸锂颗粒以及聚合物包覆层。所述聚合物包覆层包覆在所述碳酸锂颗粒的表面且包括聚合物。
在本发明的第二方面，本发明提供了一种正极添加剂的制备方法，用于制备本发明第一方面所述的正极添加剂，包括步骤：(1)将碳酸锂颗粒分散于聚合物的有机溶剂溶液中制备悬浮液；(2)通过喷雾干燥的方法处理悬浮液，即得到正极添加剂。
在本发明的第三方面，本发明提供了一种正极片，其包括正极集流体以及正极膜片。所述正极膜片设置于所述正极集流体上，且包括正极活性材料。其中，所述正极膜片还包括发明第一方面所述的正极添加剂。在本发明的第四方面，本发明提供了一种锂离子二次电池，其包括本发明第三方面所述的正极片。
相对于现有技术，本发明的有益效果为：
本发明的正极添加剂成本低廉、制备方法简单，将其应用在锂离子二次电池中时能在不影响锂离子二次电池的电性能的基础上大幅度提升锂离子二次电池安全性能。
具体实施方式
下面详细说明根据本发明的正极添加剂及其制备方法、正极片及锂离子二次电池。
首先说明根据本发明第一方面的正极添加剂。
根据本发明第一方面的正极添加剂包括改性碳酸锂。所述改性碳酸锂包括碳酸锂颗粒以及聚合物包覆层。所述聚合物包覆层包覆在所述碳酸锂颗粒的表面且包括聚合物。
在根据本发明第一方面所述的正极添加剂中，通过对普通碳酸锂颗粒进行聚合物表面包覆改性，聚合物包覆层控制碳酸锂颗粒与极片的电子电阻和离子电阻，使碳酸锂颗粒周边区域的局部电压高于极片整体电压，通过控制碳酸锂颗粒周边区域的局部电压极化使锂离子二次电池整体未达到起始降解电压时提前使碳酸锂颗粒分解，从而能根据应用的锂离子二次电池实际需 求，在较大范围内调整碳酸锂颗粒的起始降解电压，且聚合物表面包覆改性不会影响碳酸锂颗粒在极片中的电子传导与离子传导。
在根据本发明第一方面所述的正极添加剂中，所述碳酸锂颗粒的平均粒径(即D50)为20nm～20μm。所述碳酸锂颗粒的平均粒径过小不利于碳酸锂颗粒在正极浆料中的分散，所述碳酸锂颗粒的平均粒径过大则会因影响正极片电子传导及离子传导，从而影响锂离子二次电池的电性能。优选地，所述碳酸锂颗粒的粒径为100nm～5μm。
在根据本发明第一方面所述的正极添加剂中，所述聚合物可选自偏氟乙烯-六氟丙烯共聚物(PVDF-HFP)、聚偏氟乙烯(PVDF)、聚丙烯腈(PAN)、聚甲基丙烯酸甲酯(PMMA)、聚丙烯酸(PAA)、聚环氧乙烷(PEO)、聚乙烯(PE)、聚丙烯(PP)、聚四氟乙烯(PTFE)、乙烯-丙烯-丁二烯三元共聚物(EDPM)中的一种或几种。
在根据本发明第一方面所述的正极添加剂中，聚合物的重均分子量为50000～500000。优选地，聚合物的重均分子量为100000～250000。
在根据本发明第一方面所述的正极添加剂中，所述聚合物包覆层的质量为所述碳酸锂颗粒的质量的1％～50％。
其次说明根据本发明第二方面的正极添加剂的制备方法。
根据本发明第二方面的正极添加剂的制备方法，用于制备本发明第一方面所述的正极添加剂，包括步骤：(1)将碳酸锂颗粒分散于聚合物的有机溶剂溶液中制备悬浮液；(2)通过喷雾干燥的方法处理悬浮液，得到正极添加剂。
在根据本发明第二方面所述的正极添加剂的制备方法中，在步骤(1)中，有机溶剂可选自醚类、酯类、腈类、酰胺类、醇类以及卤代烷烃中的一种或几种。具体地，所述醚类可选自乙醚、四氢呋喃(THF)中的一种或两种；所述酯类可选自乙酸乙酯、甲酸甲酯、邻苯二甲酸二甲酯中的一种或几种；所述腈类可选自乙腈；所述酰胺类可选自N-甲基吡咯烷酮、N,N-二甲基甲酰胺中的一种或两种；所述醇类可选自甲醇、乙醇、异丙醇中的一种或几种；所述卤代烷烃可选自二氯甲烷、三氯甲烷、二氯乙烷中的一种或几种。
再次说明根据本发明第三方面的正极片。
根据本发明第三方面的正极片包括正极集流体以及正极膜片。所述正极膜片设置于正极集流体上，且包括正极活性材料。所述正极膜片还包括根据本发明第一方面所述的正极添加剂。
在根据本发明第三方面所述的正极片中，所述正极膜片还包括导电剂。所述导电剂可选自石墨、乙炔黑、导电炭黑、超导炭黑、石墨烯、碳纳米管、导电纤维、金属粉末、有机导电聚合物中的一种或几种。所述石墨可选自天然石墨或人造石墨。所述乙炔黑可选自科琴黑。所述导电纤维可选自碳纤维或金属纤维。所述金属粉末可选自铜粉或镍粉。所述有机导电聚合物可选自聚亚苯基衍生物。
在根据本发明第三方面所述的正极片中，所述正极膜片还包括粘结剂。所述粘结剂可选自聚偏氟乙烯、聚乙烯醇、聚氨酯、聚丙烯酸酯、丁基橡胶、环氧树脂、醋酸乙烯树脂、氯化橡胶中的一种或几种。
在根据本发明第三方面所述的正极片中，所述正极活性材料可选自层状结构的锂金属氧化物、不含锂的金属氧化物、尖晶石结构的锂金属氧化物、锂金属磷酸盐、锂金属氟化硫酸盐、锂金属钒酸盐中的一种或几种。所述层状结构的锂金属氧化物可选自钴酸锂(LCO)、镍钴锰三元材料(NCM)、镍钴铝三元材料(NCA)。所述不含锂的金属氧化物可选自V2O5或MnO2。所述尖晶石结构的锂金属氧化物可选自锰酸锂(LiMn2O4)。所述锂金属磷酸盐可选自磷酸铁锂(LFP)。所述锂金属氟化硫酸盐可选自氟化硫酸钴锂(LiCoFSO4)。所述锂金属钒酸盐可选自钒酸镍锂(LiNiVO4)。
根据本发明第三方面所述的正极片中，所述正极集流体可选自不锈钢、镍、钛、碳、铝、导电树脂、涂布有镍或钛的铜片、涂布有镍或钛的不锈钢片中的一种或几种。
在根据本发明第一方面所述的正极片中，所述正极添加剂的质量为所述正极活性材料的质量的0.5％～10％。所述正极添加剂的质量过高会降低正极片的能量密度，影响锂离子二次电池的功率性能且增加锂离子二次电池正常使用时的产气量。所述正极添加剂的质量过低会使得电流阻断装置在锂离子二次电池过充滥用时无法及时切断充电回路，无法有效控制锂离子二次电池的热失控。优选地，所述正极添加剂的质量为所述正极活性材料的质量的 1％～5％。
接下来说明根据本发明第四方面的锂离子二次电池，其包括本发明第三方面所述的正极片。
根据本发明第四方面的锂离子二次电池还包括负极片、隔离膜以及电解液。隔离膜间隔于正负极片之间。
在根据本发明第四方面所述的离子二次电池中，所述负极片包括负极活性材料。所述负极活性材料可选自人造石墨、天然石墨、Si单质、Sn单质、SiOx(0<x<2)、SnOy(0<y<2)、Si合金(即Si与Ti、Fe、Co、Ni、Cu中的一种或几种形成的合金材料)、Sn合金(即Sn与Ti、Fe、Co、Ni、Cu中的一种或几种形成的合金材料)中的一种或几种。
在根据本发明第四方面所述的离子二次电池中，所述电解液包括非水有机溶剂和溶解在其中的电解质。优选地，所述非水有机溶剂可选自碳酸亚乙酯、碳酸亚丙酯、碳酸二甲酯、碳酸二乙酯、碳酸甲乙酯、亚乙烯基碳酸酯中的一种或几种。所述电解质可选自LiPF6、LiBF4、LiCl、LiAlCl4、LiSbF6、LiSCN、LiCF3SO3、LiCF3CO2、LiN(CF3SO2)、LiAsF6、LiBC4O8中的一种或几种。
在根据本发明第四方面所述的离子二次电池中，隔离膜的具体种类并不受到具体的限制，可以是现有锂离子二次电池中使用的任何隔离膜材料。优选地。所述隔离膜选自聚乙烯、聚丙烯、聚偏氟乙烯以及它们的多层复合膜。
下面结合实施例，进一步阐述本申请。应理解，这些实施例仅用于说明本申请而不用于限制本申请的范围。
实施例1
(1)正极添加剂的制备
将碳酸锂颗粒(D50＝20μm)分散于PVDF-HFP(重均分子量＝500000)的无水THF溶液(PVDF-HFP浓度为10wt％)中得到悬浮液，加热到50℃并保温搅拌1小时，之后通过喷雾干燥的方法处理悬浮液，得到表面包覆有聚合物包覆层的碳酸锂颗粒，即得到正极添加剂改性碳酸锂，其中聚合物包 覆层的质量为碳酸锂颗粒的质量的1％。
(2)正极片的制备
将粘结剂PVDF溶于N-甲基吡咯烷酮中，之后向其中加入正极活性材料NCM(111)、正极添加剂、导电剂乙炔黑，充分混合后得到正极浆料，其中，PVDF、NCM(111)、正极添加剂、乙炔黑的质量比为3:100:10:2。然后将正极浆料涂覆于12μm厚的正极集流体铝箔的正反两面上，然后在85℃下鼓风干燥20h，冷压卷起，得到正极片。
(3)负极片的制备
将负极活性材料人造石墨、导电剂乙炔黑、粘结剂丁苯橡胶乳液(SBR)、增稠剂羧甲基纤维素钠(CMC)按照质量比97:1:1.5:0.5溶于溶剂去离子水中制成负极浆料，之后涂覆在负极集流体铜箔的正反两面上，然后在110℃下鼓风干燥20h，冷压卷起，得到负极片。
(4)电解液的制备
在含水量<10ppm的氩气气氛手套箱中，将碳酸亚乙酯、碳酸二乙酯、碳酸甲乙酯、亚乙烯基碳酸酯按照质量比为8:85:5:2进行混合后，得到混合非水有机溶剂，再将充分干燥的锂盐LiPF6溶解于上述混合非水有机溶剂中，搅拌均匀后，获得电解液，其中LiPF6与混合非水有机溶剂的质量比为8:92。
(5)锂离子二次电池的制备
将正极片、隔离膜(PE膜)、负极片按顺序叠好，使隔离膜处于正负极片之间起到隔离的作用，然后卷绕得到裸电芯；将裸电芯置于外包装箔中，将上述制备好的电解液注入到干燥后的电芯中，然后经过真空封装、静置、化成、整形等工序，得到锂离子二次电池。
实施例2
依照实施例1的方法制备锂离子二次电池，区别在于：
(1)正极添加剂的制备
将碳酸锂颗粒(D50＝5μm)分散于PVDF-HFP(重均分子量＝100000)的乙腈溶液(PVDF-HFP浓度为20wt％)中得到悬浮液，加热到50℃并保温搅拌1小时，之后通过喷雾干燥的方法处理悬浮液，得到表面包覆有聚合物包覆层的碳酸锂颗粒，即得到正极添加剂改性碳酸锂，其中聚合物包覆层的 质量为碳酸锂颗粒的质量的10％。
(2)正极片的制备
将粘结剂PVDF溶于N-甲基吡咯烷酮中，之后向其中加入正极活性材料NCM(523)、正极添加剂、导电剂乙炔黑，充分混合后得到正极浆料，其中，PVDF、NCM(523)、正极添加剂、乙炔黑的质量比为3:100:1:2。然后将正极浆料涂覆于12μm厚的正极集流体铝箔的正反两面上，然后在85℃下鼓风干燥20h，冷压卷起，得到正极片。
实施例3
依照实施例1的方法制备锂离子二次电池，区别在于：
(1)正极添加剂的制备
将碳酸锂颗粒(D50＝500nm)分散于PVDF-HFP(重均分子量＝100000)的乙腈溶液(PVDF-HFP浓度为20wt％)中得到悬浮液，加热到50℃并保温搅拌1小时，之后通过喷雾干燥的方法处理悬浮液，得到表面包覆有聚合物包覆层的碳酸锂颗粒，即得到正极添加剂改性碳酸锂，其中聚合物包覆层的质量为碳酸锂颗粒的质量的1％。
(2)正极片的制备
将粘结剂PVDF溶于N-甲基吡咯烷酮中，之后向其中加入正极活性材料NCM(622)、正极添加剂、导电剂乙炔黑，充分混合后得到正极浆料，其中，PVDF、NCM(622)、正极添加剂、乙炔黑的质量比为3:100:0.5:2。然后将正极浆料涂覆于12μm厚的正极集流体铝箔的正反两面上，然后在85℃下鼓风干燥20h，冷压卷起，得到正极片。
实施例4
依照实施例1的方法制备锂离子二次电池，区别在于：
(1)正极添加剂的制备
将碳酸锂颗粒(D50＝1μm)分散于PAN(重均分子量＝200000)的乙腈溶液(PVDF-HFP浓度为5wt％)中得到悬浮液，加热到50℃并保温搅拌1小时，之后通过喷雾干燥的方法处理悬浮液，得到表面包覆有聚合物包覆层的碳酸锂颗粒，即得到正极添加剂改性碳酸锂，其中聚合物包覆层的质量为 碳酸锂颗粒的质量的5％。
(2)正极片的制备
将粘结剂PVDF溶于N-甲基吡咯烷酮中，之后向其中加入正极活性材料钴酸锂、正极添加剂、导电剂乙炔黑，充分混合后得到正极浆料，其中，PVDF、钴酸锂、正极添加剂、乙炔黑的质量比为3:100:5:2。然后将正极浆料涂覆于12μm厚的正极集流体铝箔的正反两面上，然后在85℃下鼓风干燥20h，冷压卷起，得到正极片。
实施例5
依照实施例1的方法制备锂离子二次电池，区别在于：
(1)正极添加剂的制备
将碳酸锂颗粒(D50＝1μm)分散于PAA(重均分子量＝250000)的乙醇溶液(PVDF-HFP浓度为2wt％)中得到悬浮液，加热到50℃并保温搅拌1小时，之后通过喷雾干燥的方法处理悬浮液，得到表面包覆有聚合物包覆层的碳酸锂颗粒，即得到正极添加剂改性碳酸锂，其中聚合物包覆层的质量为碳酸锂颗粒的质量的10％。
(2)正极片的制备
将粘结剂PVDF溶于N-甲基吡咯烷酮中，之后向其中加入正极活性材料NCA、正极添加剂、导电剂乙炔黑，充分混合后得到正极浆料，其中，PVDF、NCA、正极添加剂、乙炔黑的质量比为3:100:3:2。然后将正极浆料涂覆于12μm厚的正极集流体铝箔的正反两面上，然后在85℃下鼓风干燥20h，冷压卷起，得到正极片。
对比例1
依照实施例1的方法制备锂离子二次电池，区别在于，正极添加剂为普通碳酸锂(即没有包覆层的碳酸锂)。
对比例2
依照实施例2的方法制备锂离子二次电池，区别在于，正极添加剂为普通碳酸锂(即没有包覆层的碳酸锂)。
对比例3
依照实施例3的方法制备锂离子二次电池，区别在于，正极添加剂为普通碳酸锂(即没有包覆层的碳酸锂)。
对比例4
依照实施例4的方法制备锂离子二次电池，区别在于，正极添加剂为普通碳酸锂(即没有包覆层的碳酸锂)。
对比例5
依照实施例5的方法制备锂离子二次电池，，区别在于，正极添加剂为普通碳酸锂(即没有包覆层的碳酸锂)。
最后给出实施例1-5以及对比例1-5的性能测试过程以及测试结果。
(1)锂离子二次电池的倍率性能测试
在25℃将锂离子二次电池静置5min，以0.5C恒流充电至电压为4.2V，之后以4.2V恒压充电至电流为0.05C，此时锂离子二次电池达到满充状态(100％SOC)，静置5min，再以0.1C和1C分别恒流放电至电压为3.0V。每组均取4个锂离子二次电池进行测试，取平均值。
锂离子二次电池的1C/0.1C放电倍率性能(％)＝锂离子二次电池在1C下的第10次循环放电电量/锂离子二次电池在0.1C下的第10次循环的放电电量×100％。
(2)锂离子二次电池的安全性能测试
在25℃将锂离子二次电池静置5min，以0.5C恒流充电至电压为4.2V，之后以4.2V恒压充电至电流为0.05C，此时锂离子二次电池达到满充状态(100％SOC)，静置5min，再以0.1C的倍率充电至电压为5V，然后以5V恒压继续充电，直至锂离子二次电池的电流阻断装置发挥作用，得到过充中止时的锂离子二次电池的电压(即过充失效电压)和SOC状态(即过充失效SOC)。每组取4个锂离子二次电池进行测试，取平均值。
Figure PCTCN2017093546-appb-000001
从表1中可以看出，实施例1-5的锂离子二次电池的倍率性能与对比例1-5的锂离子二次电池的倍率性能无明显差别，这表明本发明的正极添加剂的使用对锂离子二次电池的电性能基本无影响。
从表1中还可以看出，实施例1-5的锂离子二次电池的安全性能较对比例1-5有很大改善，锂离子二次电池的过充失效电压和过充失效SOC降低。对比例1-5的锂离子二次电池的过充失效电压和过充失效SOC较高，甚至在电流阻断装置发挥作用前已发生热失控。这表明本发明的正极添加剂相对于普通碳酸锂而言对电压更加敏感，在锂离子二次电池发生过充时，能及时分解产生气体，增加电池内压，使压力检测式的电流阻断装置发挥作用，从而有效防止锂离子二次电池的热失控。
根据上述说明书的揭示，本申请所属领域的技术人员还可以对上述实施方式进行适当的变更和修改。因此，本申请并不局限于上面揭示和描述的具体实施方式，对本申请的一些修改和变更也应当落入本申请的权利要求的保护范围内。

Claims (12)

  1. 一种正极添加剂，其特征在于，所述正极添加剂包括改性碳酸锂，所述改性碳酸锂包括：
    碳酸锂颗粒；以及
    聚合物包覆层，包覆在所述碳酸锂颗粒的表面且包括聚合物。
  2. 根据权利要求1所述的正极添加剂，其特征在于，所述碳酸锂颗粒的平均粒径为20nm～20μm，优选为100nm～5μm。
  3. 根据权利要求1所述的正极添加剂，其特征在于，所述聚合物选自偏氟乙烯-六氟丙烯共聚物、聚偏氟乙烯、聚丙烯腈、聚甲基丙烯酸甲酯、聚丙烯酸、聚环氧乙烷、聚乙烯、聚丙烯、聚四氟乙烯、乙烯-丙烯-丁二烯三元共聚物中的一种或几种。
  4. 根据权利要求3所述的正极添加剂，其特征在于，所述聚合物的重均分子量为50000～500000，优选为100000～250000。
  5. 根据权利要求1所述的正极添加剂，其特征在于，所述聚合物包覆层的质量为所述碳酸锂颗粒的质量的1％～50％。
  6. 一种正极添加剂的制备方法，用于制备权利要求1-5中任一项所述的正极添加剂，其特征在于，包括步骤：
    将碳酸锂颗粒分散于聚合物的有机溶剂溶液中制备悬浮液；
    通过喷雾干燥的方法处理悬浮液，即得到正极添加剂。
  7. 一种正极片，包括：
    正极集流体；以及
    正极膜片，设置于正极集流体上，且包括正极活性材料；
    其特征在于，
    所述正极膜片还包括根据权利要求1-5中任一项所述的正极添加剂。
  8. 根据权利要求7所述的正极片，其特征在于，所述正极膜片还包括导电剂，所述导电剂选自石墨、乙炔黑、导电炭黑、超导炭黑、石墨烯、碳纳米管、导电纤维、金属粉末、有机导电聚合物中的一种或几种。
  9. 根据权利要求7或8所述的正极片，其特征在于，所述正极膜片还包括粘结剂，所述粘结剂选自聚偏氟乙烯、聚乙烯醇、聚氨酯、聚丙烯酸酯、丁基橡胶、环氧树脂、醋酸乙烯树脂、氯化橡胶中的一种或几种。
  10. 根据权利要求7所述的正极片，其特征在于，所述正极活性材料选自层状结构的锂金属氧化物、不含锂的金属氧化物、尖晶石结构的锂金属氧化物、锂金属磷酸盐、锂金属氟化硫酸盐、锂金属钒酸盐中的一种或几种。
  11. 根据权利要求7所述的正极片，其特征在于，所述正极添加剂的质量为所述正极活性材料的质量的0.5％～10％，优选为1％～5％。
  12. 一种锂离子二次电池，其特征在于，包括根据权利要求7-11中任一项所述的正极片。
PCT/CN2017/093546 2016-08-25 2017-07-19 正极添加剂及其制备方法、正极片及锂离子二次电池 WO2018036309A1 (zh)

Priority Applications (2)

Application Number Priority Date Filing Date Title
EP17842732.4A EP3480878A4 (en) 2016-08-25 2017-07-19 POSITIVE ELECTRODE ADDITIVE AND PRODUCTION METHOD THEREFOR, POSITIVE ELECTRODE PLATE AND LITHIUM-ION SECONDARY BATTERY
US16/267,009 US10840501B2 (en) 2016-08-25 2019-02-04 Positive electrode additive and preparation method therefor, positive electrode plate and secondary lithium ion battery

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
CN201610720562.2 2016-08-25
CN201610720562.2A CN107785578B (zh) 2016-08-25 2016-08-25 正极添加剂及其制备方法、正极片及锂离子二次电池

Related Child Applications (1)

Application Number Title Priority Date Filing Date
US16/267,009 Continuation US10840501B2 (en) 2016-08-25 2019-02-04 Positive electrode additive and preparation method therefor, positive electrode plate and secondary lithium ion battery

Publications (1)

Publication Number Publication Date
WO2018036309A1 true WO2018036309A1 (zh) 2018-03-01

Family

ID=61245423

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/CN2017/093546 WO2018036309A1 (zh) 2016-08-25 2017-07-19 正极添加剂及其制备方法、正极片及锂离子二次电池

Country Status (4)

Country Link
US (1) US10840501B2 (zh)
EP (1) EP3480878A4 (zh)
CN (1) CN107785578B (zh)
WO (1) WO2018036309A1 (zh)

Families Citing this family (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US11251430B2 (en) 2018-03-05 2022-02-15 The Research Foundation For The State University Of New York ϵ-VOPO4 cathode for lithium ion batteries
US10411752B1 (en) 2018-10-29 2019-09-10 Globalfoundries Inc. Methods, apparatus, and system for high-bandwidth on-mold antennas
CN111162247B (zh) * 2018-11-07 2021-08-17 宁德时代新能源科技股份有限公司 正极极片及锂离子二次电池
CN111599984A (zh) * 2019-02-21 2020-08-28 贝特瑞新材料集团股份有限公司 一种正极片和包含该正极片的锂离子电池及其制备方法
DE102019119791A1 (de) * 2019-07-22 2021-01-28 Bayerische Motoren Werke Aktiengesellschaft Kathoden-Aktivmaterial, Kathode für eine Lithiumionen-Batterie, Lithiumionen-Batterie und Verwendung von Lithiumcarbonat in einer Lithiumionen-Batterie
CN113130972A (zh) * 2020-01-16 2021-07-16 微宏动力系统（湖州）有限公司 一种锂离子电池
CN112054202A (zh) * 2020-09-10 2020-12-08 辽宁九夷锂能股份有限公司 一种高能量大倍率锂电池正极添加剂及其制备方法和含有正极添加剂的正极片
CN113285071B (zh) * 2021-05-14 2022-04-26 合肥国轩高科动力能源有限公司 磷酸铁锂及其制备方法与应用

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104900907A (zh) * 2015-06-12 2015-09-09 宁德时代新能源科技有限公司 一种锂离子电池浆料的制备方法
CN105514417A (zh) * 2016-01-28 2016-04-20 先进储能材料国家工程研究中心有限责任公司 一种高安全锂离子电池正极浆料及其制备方法

Family Cites Families (28)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1245321A (en) * 1968-01-20 1971-09-08 Huels Chemische Werke Ag Polymerisation process
JP3396076B2 (ja) * 1994-03-17 2003-04-14 日本化学工業株式会社 リチウム二次電池用コバルト酸リチウム系正極活物質の製造方法
US20050053834A1 (en) * 2003-09-04 2005-03-10 Advanced Battery Technology, Ltd. Positive electrode material and method
JP4636341B2 (ja) 2008-04-17 2011-02-23 トヨタ自動車株式会社 リチウム二次電池およびその製造方法
WO2011077932A1 (ja) * 2009-12-22 2011-06-30 Jx日鉱日石金属株式会社 リチウムイオン電池用正極活物質、リチウムイオン電池用正極及びそれを用いたリチウムイオン電池、並びに、リチウムイオン電池用正極活物質前駆体
US8658312B2 (en) * 2010-03-31 2014-02-25 Panasonic Corporation Positive electrode for lithium ion battery, fabrication method thereof, and lithium ion battery using the same
JP5578280B2 (ja) * 2011-05-26 2014-08-27 トヨタ自動車株式会社 被覆活物質およびリチウム固体電池
WO2014104234A1 (ja) * 2012-12-28 2014-07-03 Ａｇｃセイミケミカル株式会社 表面修飾リチウム含有複合酸化物粒子、該粒子を用いた正極及び非水電解質二次電池
CN105340123B (zh) 2013-07-01 2018-01-05 三洋电机株式会社 非水电解质二次电池
CN103367714B (zh) * 2013-07-09 2015-05-13 宁德新能源科技有限公司 锂离子电池用石墨负极极片及其制备方法
US11721831B2 (en) * 2013-08-30 2023-08-08 Sila Nanotechnologies, Inc. Electrolyte or electrode additives for increasing metal content in metal-ion batteries
US20150099193A1 (en) * 2013-10-04 2015-04-09 Asahi Kasei Kabushiki Kaisha Electrolytic solution for non-aqueous energy storage device and lithium ion secondary battery
CN103633385A (zh) 2013-11-15 2014-03-12 江苏天鹏电源有限公司 一种用于解决锂离子电池整组短路问题的方法
JPWO2015098471A1 (ja) * 2013-12-25 2017-03-23 旭化成株式会社 シリル基含有化合物を含む電解液添加用組成物、該組成物を含む非水蓄電デバイス用電解液、及び該電解液を含むリチウムイオン二次電池
EP3103151B1 (en) * 2014-02-03 2019-09-04 Ramot at Tel-Aviv University Ltd. Electrode compositions and alkali metal batteries comprising same
CN106716685B (zh) * 2014-09-30 2020-04-21 三洋电机株式会社 非水电解质二次电池用正极和使用其的非水电解质二次电池
CN104466135B (zh) * 2014-12-15 2017-01-25 中信大锰矿业有限责任公司大新锰矿分公司 一种导电聚合物包覆镍钴锰酸锂正极材料的方法
US9780349B2 (en) * 2015-05-21 2017-10-03 Nanotek Instruments, Inc. Carbon matrix- and carbon matrix composite-based dendrite-intercepting layer for alkali metal secondary battery
US10497968B2 (en) * 2016-01-04 2019-12-03 Global Graphene Group, Inc. Solid state electrolyte for lithium secondary battery
KR101961365B1 (ko) * 2016-01-14 2019-07-17 주식회사 엘지화학 리튬 이차전지용 음극 활물질 및 제조방법
WO2017126697A1 (ja) * 2016-01-22 2017-07-27 旭化成株式会社 非水系リチウム型蓄電素子
KR101959701B1 (ko) * 2016-01-22 2019-03-18 아사히 가세이 가부시키가이샤 리튬 이온 2 차 전지
CN105810885B (zh) * 2016-04-27 2018-08-21 宁德时代新能源科技股份有限公司 一种正极极片及锂离子电池
JP6519575B2 (ja) * 2016-12-07 2019-05-29 トヨタ自動車株式会社 リチウムイオン二次電池
US10483533B2 (en) * 2017-04-10 2019-11-19 Global Graphene Group, Inc. Encapsulated cathode active material particles, lithium secondary batteries containing same, and method of manufacturing
JP6870505B2 (ja) * 2017-07-05 2021-05-12 三洋電機株式会社 非水電解質二次電池
KR102160572B1 (ko) * 2017-07-26 2020-09-28 주식회사 엘지화학 리튬이차전지용 양극 및 이를 포함하는 리튬이차전지
KR102374121B1 (ko) * 2017-08-02 2022-03-14 삼성전자주식회사 나노입자형 구조체에 내장된 위상구조 양자 프레임워크, 이를 포함하는 복합음극활물질, 음극, 리튬전지, 반도체, 소자 및 이의 제조 방법

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104900907A (zh) * 2015-06-12 2015-09-09 宁德时代新能源科技有限公司 一种锂离子电池浆料的制备方法
CN105514417A (zh) * 2016-01-28 2016-04-20 先进储能材料国家工程研究中心有限责任公司 一种高安全锂离子电池正极浆料及其制备方法

Also Published As

Publication number Publication date
CN107785578B (zh) 2019-06-11
EP3480878A4 (en) 2020-01-22
US20190207204A1 (en) 2019-07-04
US10840501B2 (en) 2020-11-17
CN107785578A (zh) 2018-03-09
EP3480878A1 (en) 2019-05-08

Similar Documents

Publication Publication Date Title
WO2018036309A1 (zh) 正极添加剂及其制备方法、正极片及锂离子二次电池
CN109616614B (zh) 负极极片和使用其的电化学装置和电子装置
WO2022141448A1 (zh) 电化学装置、电子装置及电化学装置的制备方法
CN103311500A (zh) 一种锂离子电池负极极片及制作方法
WO2011001666A1 (ja) 非水電解質二次電池用正極及びその製造方法並びに非水電解質二次電池
KR101697008B1 (ko) 리튬 이차전지
JP2015179565A (ja) 非水電解質電池用電極、非水電解質二次電池及び電池パック
WO2022141508A1 (zh) 一种电化学装置和电子装置
WO2022140982A1 (zh) 一种负极极片、包含该负极极片的电化学装置及电子装置
CN113130894A (zh) 负极活性材料及使用其的电化学装置和电子装置
JP6808948B2 (ja) 非水系リチウムイオン二次電池用負極、その製法及び非水系リチウムイオン二次電池
WO2011070748A1 (ja) 非水電解質二次電池及びその充電方法
US8877380B2 (en) Positive active material, method of preparing the same, and lithium battery including the positive active material
WO2022120833A1 (zh) 一种电化学装置和电子装置
WO2022198651A1 (zh) 一种正极极片、包含该正极极片的电化学装置和电子装置
JP2023538082A (ja) 負極およびこれを含む二次電池
WO2021195913A1 (zh) 负极材料、负极极片、电化学装置和电子装置
WO2023120503A1 (ja) 二次電池用正極およびその製造方法、ならびに二次電池
WO2022198614A1 (zh) 负极材料及其制备方法、电化学装置及电子装置
JP2010010093A (ja) 二次電池用電極群の製造方法および二次電池の製造方法
WO2022198667A1 (zh) 一种正极极片、包含该正极极片的电化学装置和电子装置
JP2013137939A (ja) 非水電解質二次電池
JP2010146887A (ja) 非水系二次電池用電極とその製造方法および非水系二次電池
CN115995604B (zh) 复合电解质膜、电化学装置以及电子设备
CN114094188B (zh) 一种电化学装置及包含该电化学装置的电子装置

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 17842732

Country of ref document: EP

Kind code of ref document: A1

ENP Entry into the national phase

Ref document number: 2017842732

Country of ref document: EP

Effective date: 20190130

NENP Non-entry into the national phase

Ref country code: DE