WO2021088166A1 - 正极补锂材料、包含正极补锂材料的正极及其制备方法 - Google Patents

正极补锂材料、包含正极补锂材料的正极及其制备方法 Download PDF

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WO2021088166A1
WO2021088166A1 PCT/CN2019/122055 CN2019122055W WO2021088166A1 WO 2021088166 A1 WO2021088166 A1 WO 2021088166A1 CN 2019122055 W CN2019122055 W CN 2019122055W WO 2021088166 A1 WO2021088166 A1 WO 2021088166A1
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positive electrode
lithium
material layer
active material
lithium supplement
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PCT/CN2019/122055
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English (en)
French (fr)
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周墨林
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宁德新能源科技有限公司
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Publication of WO2021088166A1 publication Critical patent/WO2021088166A1/zh
Priority to US17/708,129 priority Critical patent/US20220223859A1/en

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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
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
    • H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
    • 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
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/485—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy
    • 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
    • H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
    • H01M10/4235—Safety or regulating additives or arrangements in electrodes, separators or electrolyte
    • 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
    • H01M4/1391—Processes of manufacture of 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
    • H01M4/139—Processes of manufacture
    • H01M4/1397—Processes of manufacture of 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
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
    • H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
    • 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
    • H01M4/5825—Oxygenated metallic salts or polyanionic structures, e.g. borates, phosphates, silicates, olivines
    • 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
    • H01M4/621—Binders
    • H01M4/622—Binders being polymers
    • H01M4/623—Binders being polymers fluorinated polymers
    • 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
    • H01M4/624—Electric conductive fillers
    • H01M4/625—Carbon or graphite
    • 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
    • H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
    • H01M2004/028—Positive 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

  • This application relates to the field of energy storage technology, and in particular to a positive electrode lithium supplement material, a positive electrode containing the positive electrode lithium supplement material, and a preparation method thereof.
  • lithium-ion batteries Compared with lead-acid batteries, nickel-cadmium batteries and nickel-hydrogen batteries, lithium-ion batteries have the advantages of high energy density, high power density, high working voltage, good cycle performance, long life, low self-discharge and wide temperature adaptation range. Since commercialization in 1991, it has been widely used in the 3C digital field. However, with the vigorous development of smart phones and electric vehicles, the energy density and cycle life of existing lithium-ion batteries are increasingly unable to meet market demands.
  • the energy density and cycle life of lithium-ion batteries are closely related to the first coulombic efficiency and the formation of the negative solid electrolyte interface (SEI) film.
  • SEI solid electrolyte interface
  • lithium ion battery system that uses graphite as the negative electrode, about 10% of the lithium source will be consumed for the first charge; when a high specific capacity negative electrode material is used, such as alloys (silicon, tin, etc.), oxides (silicon oxide, oxide) When tin) and amorphous carbon are used as the negative electrode, the consumption of the positive electrode lithium source will further increase.
  • a high specific capacity negative electrode material such as alloys (silicon, tin, etc.), oxides (silicon oxide, oxide)
  • tin and amorphous carbon are used as the negative electrode, the consumption of the positive electrode lithium source will further increase.
  • Pre-replenishing the positive or negative electrode with lithium is an effective method to increase the energy density of lithium-ion batteries.
  • the existing lithium supplement materials mainly involve stabilized metal lithium powder or organic lithium salt, whose activity is still too high and cannot be stored stably for a long time, which increases the difficulty of operation and production risks.
  • the existing lithium supplement materials also have compatibility problems with existing solvents and binders.
  • the stabilized lithium metal powder will react with the common slurry solvent N-methylpyrrolidone (NMP).
  • the positive electrode lithium supplement material has a high potential, is compatible with the existing lithium-ion battery processing technology, and is safer and easier to operate. Therefore, it has attracted more and more attention from academia and industry.
  • the existing positive electrode lithium supplement materials such as L-lithium ascorbate, D-lithium erythorbate, lithium metabisulfite, lithium sulfite and lithium phytate, etc.
  • the present application provides a positive electrode lithium supplement material, a positive electrode containing the positive electrode lithium supplement material, and a preparation method thereof in an attempt to at least some extent solve at least one problem existing in the related field.
  • the present application provides a positive electrode lithium supplement material, which includes Li 2 M1O 2 , Li 2 M2O 3 , Li 5 Fe x M3 1-x O 4 or Li 6 Mn y M4 1-y O At least one of 4 , wherein M1 contains at least one of Ni, Mn, Cu, Fe, Cr, or Mo; wherein M2 contains at least one of Ni, Mn, Fe, Mo, Zr, Si, Cu, Cr, or Ru One; wherein M3 contains at least one of Al, Nb, Co, Mn, Ni, Mo, Ru or Cr; wherein M4 contains at least one of Ni, Fe, Cu or Ru; wherein 0 ⁇ x ⁇ 1, 0 ⁇ y ⁇ 1.
  • the first delithiation capacity of the positive electrode lithium supplement material is greater than or equal to about 300 mAh/g.
  • the median diameter D50 of the positive electrode lithium supplement material is less than or equal to about 1.5 ⁇ m.
  • the positive electrode lithium supplement material includes Li 2 NiO 2 , Li 2 MoO 3 , Li 5 FeO 4 , Li 5 Fe 0.9 Al 0.1 O 4 , Li 6 MnO 4 or Li 6 Mn 0.5 Ru 0.5 O 4 At least one of.
  • the present application also provides a positive electrode.
  • the positive electrode includes a positive electrode lithium-supplementing material layer, and the positive electrode lithium-supplementing material layer includes any one of the foregoing positive lithium-supplementing materials.
  • the thickness of the positive electrode lithium supplement material layer is less than or equal to about 10 ⁇ m.
  • the positive electrode lithium supplement material layer further includes a conductive agent and a binder, wherein the binder includes polypropylene, polyethylene, polyvinylidene fluoride, vinylidene fluoride-hexafluoropropylene, polytetrafluoroethylene or At least one of polyhexafluoropropylene, wherein the conductive agent includes at least one of conductive carbon black, carbon fiber, acetylene black, Ketjen black, graphene, or carbon nanotube.
  • the binder includes polypropylene, polyethylene, polyvinylidene fluoride, vinylidene fluoride-hexafluoropropylene, polytetrafluoroethylene or At least one of polyhexafluoropropylene
  • the conductive agent includes at least one of conductive carbon black, carbon fiber, acetylene black, Ketjen black, graphene, or carbon nanotube.
  • the weight percentage of the positive electrode lithium supplement material is about 80 wt% to about 90 wt%, and the weight percentage of the binder is about 5 wt% to about 10 wt%.
  • the weight percentage of the agent is about 5 wt% to about 10 wt%.
  • the positive electrode further includes a positive electrode active material layer, wherein the positive electrode lithium supplementing material layer is arranged on the current collector, and the positive electrode active material layer is arranged on the positive electrode lithium supplementing material layer.
  • the positive active material layer includes a positive active material, a binder, and a conductive agent, wherein the positive active material includes lithium cobaltate, lithium iron phosphate, lithium iron manganese phosphate, lithium vanadium phosphate, lithium vanadyl phosphate, At least one of lithium vanadate, lithium manganate, lithium nickelate, lithium nickel cobalt manganate, lithium-rich manganese-based materials, or lithium nickel cobalt aluminate, wherein the binder includes fluorine-containing resin, polypropylene resin, and fiber type At least one of adhesive, rubber type adhesive or polyimide type adhesive, wherein the conductive agent includes at least one of conductive carbon black, carbon fiber, acetylene black, Ketjen black, graphene or carbon nanotube One kind.
  • the positive active material includes lithium cobaltate, lithium iron phosphate, lithium iron manganese phosphate, lithium vanadium phosphate, lithium vanadyl phosphate, At least one of lithium vanadate, lithium manga
  • the weight percentage of the positive electrode active material is about 80wt% to about 98wt%
  • the weight percentage of the binder is about 0.5wt% to about 10wt%
  • the conductive agent The weight percentage is about 0.5 wt% to about 10 wt%.
  • the positive electrode lithium supplement material in the positive electrode lithium supplement material layer accounts for about 1 wt% to about 10 wt% of the positive electrode active material in the positive electrode active material layer.
  • the present application also provides a method for preparing a positive electrode.
  • the method includes: depositing or coating any one of the above-mentioned positive electrode lithium supplement materials on a current collector; and depositing or coating the positive electrode with the positive electrode.
  • the current collector of the lithium replenishing material is dried, and then the positive electrode active material is coated.
  • the present application also provides an electrochemical device, which includes any one of the above-mentioned positive electrodes or the positive electrode prepared by the above-mentioned method.
  • the present application also provides an electronic device, which includes any one of the electrochemical devices described above.
  • the terms “approximately”, “substantially”, “substantially” and “about” are used to describe and illustrate small changes.
  • the term can refer to an example in which the event or situation occurs precisely and an example in which the event or situation occurs very closely.
  • the term can refer to a range of variation less than or equal to ⁇ 10% of the stated value, such as less than or equal to ⁇ 5%, less than or equal to ⁇ 4%, less than or equal to ⁇ 3%, Less than or equal to ⁇ 2%, less than or equal to ⁇ 1%, less than or equal to ⁇ 0.5%, less than or equal to ⁇ 0.1%, or less than or equal to ⁇ 0.05%.
  • the difference between two values is less than or equal to ⁇ 10% of the average value of the value (for example, less than or equal to ⁇ 5%, less than or equal to ⁇ 4%, less than or equal to ⁇ 3%, less than Or equal to ⁇ 2%, less than or equal to ⁇ 1%, less than or equal to ⁇ 0.5%, less than or equal to ⁇ 0.1%, or less than or equal to ⁇ 0.05%), then the two values can be considered "substantially" the same.
  • a list of items connected by the terms “at least one of”, “at least one of”, “at least one of” or other similar terms may mean the listed items Any combination of. For example, if items A and B are listed, then the phrase “at least one of A and B” means only A; only B; or A and B. In another example, if items A, B, and C are listed, then the phrase "at least one of A, B, and C” means only A; or only B; only C; A and B (excluding C); A and C (exclude B); B and C (exclude A); or all of A, B, and C.
  • Project A can contain a single element or multiple elements.
  • Project B can contain a single element or multiple elements.
  • Project C can contain a single element or multiple elements.
  • This application provides a positive electrode lithium supplement material, a positive electrode including the positive electrode lithium supplement material and a preparation method thereof, and also provides an electrochemical device and an electronic device including the positive electrode.
  • This application provides a positive electrode lithium supplement material, which includes at least one of Li 2 M1O 2 , Li 2 M2O 3 , Li 5 Fe x M3 1-x O 4 or Li 6 Mn y M4 1-y O 4 ,
  • M1 contains at least one of Ni, Mn, Cu, Fe, Cr or Mo
  • M2 contains at least one of Ni, Mn, Fe, Mo, Zr, Si, Cu, Cr or Ru
  • M3 contains Al At least one of, Nb, Co, Mn, Ni, Mo, Ru or Cr
  • M4 contains at least one of Ni, Fe, Cu or Ru; wherein 0 ⁇ x ⁇ 1, 0 ⁇ y ⁇ 1.
  • the positive electrode lithium supplement material includes Li 2 NiO 2 , Li 2 MoO 3 , Li 5 FeO 4 , Li 5 Fe 0.9 Al 0.1 O 4 , Li 6 MnO 4 or Li 6 Mn 0.5 Ru 0.5 O 4 At least one.
  • the positive electrode lithium supplement material includes Li 5 FeO 4 .
  • the positive electrode lithium supplement material includes Li 2 NiO 2 .
  • the positive electrode lithium supplement material includes Li 6 Mn 0.5 Ru 0.5 O 4 .
  • the first delithiation capacity of the positive electrode lithium supplement material is greater than or equal to about 300 mAh/g. In some embodiments, the first delithiation capacity of the positive electrode lithium supplement material is greater than or equal to about 350 mAh/g, greater than or equal to about 400 mAh/g, greater than or equal to about 500 mAh/g, or greater than or equal to about 600 mAh/g. In some embodiments, the first delithiation capacity of the positive electrode lithium supplement material is about 300 mAh/g to about 350 mAh/g, about 300 mAh/g to about 400 mAh/g, about 300 mAh/g to about 500 mAh/g, or about 300 mAh/g -About 600mAh/g, etc.
  • the median diameter D50 of the positive electrode lithium supplement material is less than or equal to about 1.5 ⁇ m. In some embodiments, the median diameter D50 of the positive electrode lithium supplement material is less than or equal to about 1.2 ⁇ m, less than or equal to about 1 ⁇ m, or less than or equal to about 0.5 ⁇ m. In some embodiments, the median particle diameter D50 of the positive electrode lithium supplement material is about 0.5 ⁇ m to about 1.5 ⁇ m, about 1 ⁇ m to about 1.5 ⁇ m, about 0.1 ⁇ m to about 1.5 ⁇ m, and the like.
  • the present application provides a positive electrode, which includes a positive electrode lithium supplement material layer, and the positive electrode lithium supplement material layer includes any one of the above positive lithium supplement materials.
  • the weight percentage of the positive electrode lithium supplement material is about 80 wt% to about 90 wt%. In some embodiments, based on the total weight of the positive electrode lithium supplement material layer, the weight percentage of the positive electrode lithium supplement material is about 80 wt% to about 85 wt%, about 80 wt% to about 90 wt%, or about 85 wt% to about 90 wt%.
  • the thickness of the positive electrode lithium supplement material layer is less than or equal to about 10 ⁇ m. In some embodiments, the thickness of the positive electrode lithium supplement material layer is less than or equal to about 5 ⁇ m, less than or equal to about 3 nm, or less than or equal to about 1 nm. In some embodiments, the thickness of the positive electrode lithium supplement material layer is about 5 ⁇ m to about 10 ⁇ m, about 1 ⁇ m to about 5 ⁇ m, about 1 ⁇ m to about 10 ⁇ m, or about 3 ⁇ m to about 10 ⁇ m.
  • the positive electrode lithium supplement material layer further includes a binder.
  • the binder includes at least one of polypropylene, polyethylene, polyvinylidene fluoride (PVDF), vinylidene fluoride-hexafluoropropylene, polytetrafluoroethylene, or polyhexafluoropropylene.
  • the binder in the positive electrode lithium supplement material layer includes polyvinylidene fluoride.
  • the weight percentage of the binder is about 5 wt% to about 10 wt%. In some embodiments, based on the total weight of the positive electrode lithium supplement material layer, the weight percentage of the binder is about 5 wt% to about 7 wt%, or about 7 wt% to about 10 wt%, etc.
  • the positive electrode lithium supplement material layer further includes a conductive agent.
  • the conductive agent includes at least one of conductive carbon black (SP), carbon fiber, acetylene black, Ketjen black, graphene, or carbon nanotube (CNT).
  • the conductive agent in the positive electrode lithium supplement material layer includes carbon nanotubes.
  • the weight percentage of the conductive agent is about 5 wt% to about 10 wt%. In some embodiments, based on the total weight of the positive electrode lithium supplement material layer, the weight percentage of the conductive agent is about 5 wt% to about 7 wt%, or about 7 wt% to about 10 wt%, etc.
  • the positive electrode further includes a positive electrode active material layer, wherein the positive electrode lithium-supplementing material layer is arranged on the current collector, and the positive electrode active material layer is arranged on the positive-electrode lithium supplementing material layer.
  • the current collector may be aluminum (Al), but it is not limited thereto.
  • the positive active material layer includes a positive active material, a binder, and a conductive agent.
  • the positive active material includes lithium cobalt oxide (LiCoO 2 ), lithium iron phosphate, lithium iron manganese phosphate, lithium vanadium phosphate, lithium vanadyl phosphate, lithium vanadate, lithium manganate, lithium nickelate, nickel cobalt At least one of lithium manganate, lithium-rich manganese-based material, or lithium nickel cobalt aluminate.
  • the positive active material includes lithium cobalt oxide with a cut-off voltage greater than or equal to about 4.45V.
  • the binder in the positive active material layer includes at least one of a fluorine-containing resin, a polypropylene resin, a fiber-type binder, a rubber-type binder, or a polyimide-type binder. In some embodiments, the binder in the positive active material layer includes polyvinylidene fluoride.
  • the conductive agent in the positive active material layer includes at least one of conductive carbon black, carbon fiber, acetylene black, Ketjen black, graphene, or carbon nanotubes. In some embodiments, the conductive agent in the positive active material layer includes conductive carbon black.
  • the weight percentage of the positive electrode active material is about 80 wt% to about 98 wt%. In some embodiments, based on the total weight of the positive active material layer, the weight percentage of the positive active material is about 80 wt to about 85 wt %, about 80 wt to about 90 wt %, about 85 wt to about 95 wt %, or about 85 wt to about 98 wt% Wait.
  • the weight percentage of the binder is about 0.5 wt% to about 10 wt%. In some embodiments, based on the total weight of the positive active material layer, the weight percentage of the binder is about 0.5 wt% to about 5 wt%, about 1 wt% to about 5 wt%, about 5 wt% to about 10 wt%, or about 1 wt%. % To about 10wt%, etc.
  • the weight percentage of the conductive agent is about 0.5 wt% to about 10 wt%. In some embodiments, based on the total weight of the positive active material layer, the weight percentage of the conductive agent is about 0.5 wt% to about 5 wt%, about 1 wt% to about 5 wt%, about 5 wt% to about 10 wt%, or about 1 wt% -About 10wt% etc.
  • the positive electrode lithium supplement material in the positive electrode lithium supplement material layer accounts for about 1 wt% to about 10 wt% of the positive electrode active material in the positive electrode active material layer. In some embodiments, the positive electrode lithium supplement material in the positive electrode lithium supplement material layer accounts for about 1wt% to about 2wt%, about 1wt% to about 5wt%, about 2wt% to about 2wt% of the positive electrode active material in the positive electrode active material layer. 5wt% or about 5wt% to about 10wt%, etc.
  • the present application also provides a method for preparing a positive electrode, which includes depositing or coating the positive electrode lithium supplement material of the present application on a current collector; and drying the current collector deposited or coated with the positive electrode lithium supplement material, and then The positive electrode active material is coated to prepare the above-mentioned positive electrode.
  • the positive electrode lithium supplement material layer is primed (coated or deposited) on the current collector, and the particle size of the positive electrode lithium supplement material and the thickness of the positive electrode lithium supplement material layer are strictly controlled to reduce the positive electrode lithium supplement material layer Polarization.
  • the positive electrode replenishing material completes all lithium removal, releasing lithium ions to supplement the active lithium consumed by the negative electrode SEI film, which improves the reversible capacity and energy density of the electrochemical device.
  • the delithiation product with poor conductivity is left to cover the current collector, which can greatly reduce the risk of micro short circuit caused by nail penetration, and improve the electrochemical device (especially It is the safety of high-energy-density lithium-ion batteries.
  • This application adopts a double-layer coating or deposition method, which can simultaneously realize the improvement of the energy density and safety of the electrochemical device.
  • the delithiation product of the positive electrode lithium supplement material of the present application has a stable structure, and the isolation layer formed in situ on the current collector after the first delithiation can greatly reduce the risk of battery nail failure.
  • the preparation method of the positive electrode of the present application is simple and easy for commercial production.
  • the electrochemical device of the present application includes any one of the above-mentioned positive electrodes of the present application.
  • the electrochemical device of the present application may include any device that undergoes an electrochemical reaction, and specific examples thereof include all kinds of primary batteries, secondary batteries, fuel cells, solar cells, or capacitors.
  • the electrochemical device is a lithium secondary battery, including a lithium metal secondary battery, a lithium ion secondary battery, a lithium polymer secondary battery, or a lithium ion polymer secondary battery.
  • the electrochemical device of the present application includes the positive electrode of the present application, a negative electrode, a separator interposed between the positive electrode and the negative electrode, and an electrolyte.
  • the electrochemical device is a lithium ion battery.
  • the negative electrode includes a negative electrode current collector and a negative electrode active material layer on the negative electrode current collector.
  • the negative active material includes a material that reversibly intercalates/deintercalates lithium ions.
  • the material that reversibly intercalates/deintercalates lithium ions includes a carbon material.
  • the carbon material may be any carbon-based negative active material commonly used in lithium ion rechargeable batteries.
  • the carbon material includes, but is not limited to: crystalline carbon, amorphous carbon, or a mixture thereof.
  • the crystalline carbon may be amorphous, flake-shaped, flake-shaped, spherical or fibrous natural graphite or artificial graphite.
  • Amorphous carbon can be soft carbon, hard carbon, mesophase pitch carbide, calcined coke and the like.
  • the negative active material includes, but is not limited to: lithium metal, structured lithium metal, natural graphite, artificial graphite, mesophase carbon microspheres (MCMB), hard carbon, soft carbon, silicon, silicon oxide ( SiO x ), silicon-carbon composite, Li-Sn alloy, Li-Sn-O alloy, Sn, SnO, SnO 2 , spinel structure lithiated TiO 2 -Li 4 Ti 5 O 12 , Li-Al alloy Or any combination thereof.
  • MCMB mesophase carbon microspheres
  • the negative electrode active material layer can be formed using a method such as a vapor deposition method, a sputtering method, or a plating method.
  • the negative electrode includes lithium metal, for example, a conductive skeleton having a spherical twisted shape and metal particles dispersed in the conductive skeleton are used to form the negative electrode active material layer.
  • the spherical stranded conductive skeleton may have a porosity of about 5% to about 85%.
  • a protective layer may be further provided on the lithium metal negative electrode active material layer.
  • the negative electrode may further include a binder.
  • the binder improves the bonding of the negative active material particles with each other and the bonding of the negative active material with the negative current collector.
  • the binder includes, but is not limited to: polyvinyl alcohol, carboxymethyl cellulose, hydroxypropyl cellulose, diacetyl cellulose, polyvinyl chloride, carboxylated polyvinyl chloride, polyfluoro Ethylene, polymers containing ethylene oxide, polyvinylpyrrolidone, polyurethane, polytetrafluoroethylene, polyvinylidene fluoride, polyethylene, polypropylene, polyacrylic acid (PAA), styrene butadiene rubber, acrylic ( Esterified styrene butadiene rubber, epoxy resin, nylon, etc.
  • PAA polyacrylic acid
  • styrene butadiene rubber acrylic ( Esterified styrene butadiene rubber, epoxy resin, nylon, etc.
  • the negative electrode can also be a conductive agent.
  • Conductive agents include, but are not limited to: carbon-based materials, metal-based materials, conductive polymers, or mixtures thereof.
  • the carbon-based material is selected from natural graphite, artificial graphite, conductive carbon black, acetylene black, Ketjen black, carbon fiber, or any combination thereof.
  • the metal-based material is selected from metal powder, metal fiber, copper, nickel, aluminum, silver.
  • the conductive polymer is a polyphenylene derivative.
  • the negative electrode current collector includes, but is not limited to: copper (Cu) foil, nickel foil, stainless steel foil, titanium foil, foamed nickel, foamed copper, conductive metal-coated polymer substrate, and any combination thereof.
  • the negative electrode can be prepared by a preparation method known in the art.
  • the negative electrode can be obtained by mixing an active material, a conductive material, and a binder in a solvent to prepare an active material composition, and coating the active material composition on a current collector.
  • the solvent may include water and the like, but is not limited thereto.
  • the isolation film includes, but is not limited to, at least one selected from polyethylene, polypropylene, polyethylene terephthalate, polyimide, and aramid.
  • polyethylene includes at least one component selected from high-density polyethylene, low-density polyethylene, and ultra-high molecular weight polyethylene.
  • polyethylene and polypropylene they have a good effect on preventing short circuits, and can improve the stability of lithium-ion batteries through the shutdown effect.
  • the electrolyte may be one or more of a gel electrolyte, a solid electrolyte, and an electrolyte, and the electrolyte includes a lithium salt and a non-aqueous solvent.
  • the lithium salt may be selected from LiPF 6 , LiBF 4 , LiAsF 6 , LiClO 4 , LiB(C 6 H 5 ) 4 , LiCH 3 SO 3 , LiCF 3 SO 3 , LiN(SO 2 CF 3 ) 2 , LiC(SO 2 CF 3 ) 3 , LiSiF 6 , LiBOB or one or more of lithium difluoroborate.
  • LiPF 6 is selected for the lithium salt because it can give high ionic conductivity and improve cycle characteristics.
  • the non-aqueous solvent may be a carbonate compound, a carboxylate compound, an ether compound, other organic solvents, or a combination thereof.
  • the carbonate compound may be a chain carbonate compound, a cyclic carbonate compound, a fluorocarbonate compound, or a combination thereof.
  • examples of chain carbonate compounds are diethyl carbonate (DEC), dimethyl carbonate (DMC), dipropyl carbonate (DPC), methyl propyl carbonate (MPC), ethylene propyl carbonate (EPC), ethyl methyl carbonate (MEC) and combinations thereof.
  • examples of the cyclic carbonate compound are ethylene carbonate (EC), propylene carbonate (PC), butylene carbonate (BC), vinyl ethylene carbonate (VEC), or a combination thereof.
  • fluorocarbonate compound examples include fluoroethylene carbonate (FEC), 1,2-difluoroethylene carbonate, 1,1-difluoroethylene carbonate, 1,1,2-tricarbonate Fluoroethylene, 1,1,2,2-tetrafluoroethylene carbonate, 1-fluoro-2-methylethylene carbonate, 1-fluoro-1-methylethylene carbonate, 1,2 carbonate -Difluoro-1-methylethylene, 1,1,2-trifluoro-2-methylethylene carbonate, trifluoromethylethylene carbonate, or a combination thereof.
  • FEC fluoroethylene carbonate
  • 1,2-difluoroethylene carbonate 1,1-difluoroethylene carbonate
  • 1,1,2-tricarbonate Fluoroethylene, 1,1,2,2-tetrafluoroethylene carbonate, 1-fluoro-2-methylethylene carbonate, 1-fluoro-1-methylethylene carbonate, 1,2 carbonate -Difluoro-1-methylethylene, 1,1,2-trifluoro-2-methylethylene carbonate, trifluoromethylethylene carbonate,
  • examples of carboxylate compounds are methyl acetate, ethyl acetate, n-propyl acetate, tert-butyl acetate, methyl propionate, ethyl propionate, propyl propionate, ⁇ -butyrolactone Ester, caprolactone, valerolactone, mevalonolactone, caprolactone, methyl formate, or combinations thereof.
  • examples of ether compounds are dibutyl ether, tetraglyme, diglyme, 1,2-dimethoxyethane, 1,2-diethoxyethane , Ethoxymethoxyethane, 2-methyltetrahydrofuran, tetrahydrofuran or a combination thereof.
  • examples of other organic solvents are dimethyl sulfoxide, 1,2-dioxolane, sulfolane, methyl sulfolane, 1,3-dimethyl-2-imidazolidinone, N-methyl -2-pyrrolidone, formamide, dimethylformamide, acetonitrile, trimethyl phosphate, triethyl phosphate, trioctyl phosphate, phosphate ester, or a combination thereof.
  • the electrochemical device manufactured from the positive electrode described in this application is suitable for electronic devices in various fields.
  • the electrochemical device of the present application is not particularly limited, and it can be used for any purpose known in the prior art.
  • the electrochemical device of the present application can be used in, but not limited to, notebook computers, pen-input computers, mobile computers, e-book players, portable phones, portable fax machines, portable copiers, portable printers, and headsets.
  • Step three first spray the positive electrode lithium supplement material layer slurry on the surface of the Al current collector, dry and roll to control its thickness to 5 ⁇ m, and then apply the positive electrode active material layer slurry on the positive electrode lithium supplement material layer, after drying A double-layer structure lithium-supplemented positive pole piece is obtained.
  • Step 5 The positive and negative pole pieces prepared above are rolled, cut, laminated, injected and encapsulated to obtain a soft-packed lithium ion battery.
  • the lithium ion battery was prepared by the method of Example 1, and the capacity test and nail penetration test were performed.
  • the lithium ion battery was prepared by the method of Example 1, and the capacity test and nail penetration test were performed.
  • Example 3 The difference between Example 3 and Example 1 is that in step 2, Li 5 FeO 4 accounts for about 10% of the weight of LiCoO 2 in the positive electrode active material layer; in step 3, the thickness of the positive electrode lithium supplement material layer is controlled to 10 ⁇ m.
  • the lithium ion battery was prepared by the method of Example 1, and the capacity test and nail penetration test were performed.
  • Example 4 The difference between Example 4 and Example 1 is that in step 4, the negative electrode active material is graphite.
  • the lithium ion battery was prepared by the method of Example 2 and the capacity test and nail penetration test were performed.
  • Example 5 The difference between Example 5 and Example 2 is that in step 2, Li 5 FeO 4 accounts for about 2% of the weight of LiCoO 2 in the positive electrode active material layer; in step 4, the negative electrode active material is graphite.
  • the lithium ion battery was prepared by the method of Example 3 and the capacity test and nail penetration test were performed.
  • Example 6 The difference between Example 6 and Example 3 is that in step 2, Li 5 FeO 4 accounts for about 5% of the weight of LiCoO 2 in the positive electrode active material layer; in step 4, the negative electrode active material is graphite.
  • the lithium ion battery was prepared by the method of Example 1, and the capacity test and nail penetration test were performed.
  • Example 7 The difference between Example 7 and Example 1 is that the lithium supplement material in step 2 is Li 2 NiO 2 , and the median diameter D50 of Li 2 NiO 2 is 1.0 ⁇ m, which accounts for approximately the LiCoO in the positive electrode active material layer. 2 10% by weight.
  • the lithium ion battery was prepared by the method of Example 1, and the capacity test and nail penetration test were performed.
  • Example 8 The difference between Example 8 and Example 1 is that the lithium supplement material in step 2 is Li 6 Mn 0.5 Ru 0.5 O 4 , and the median diameter D50 of Li 6 Mn 0.5 Ru 0.5 O 4 is 1.2 ⁇ m, which is about It accounts for 4% of the weight of LiCoO 2 in the positive electrode active material layer.
  • the negative electrode active material is graphite.
  • Step three the positive and negative pole pieces are rolled, cut, laminated, injected and packaged to obtain a soft-packed lithium ion battery.
  • a lithium ion battery was prepared by the method of Comparative Example 1, and the capacity test and nail penetration test were performed.
  • Comparative Example 2 The difference between Comparative Example 2 and Comparative Example 1 is that in step 2, the negative electrode active material is graphite.
  • a lithium ion battery was prepared by the method of Comparative Example 1, and the capacity test and nail penetration test were performed.
  • a lithium ion battery was prepared by the method of Comparative Example 1, and the capacity test and nail penetration test were performed.
  • a lithium ion battery was prepared by the method of Comparative Example 1, and the capacity test and nail penetration test were performed.
  • Comparative Example 3 The method of Comparative Example 3 was used to prepare a lithium-ion battery and conduct a capacity test and a nail penetration test.
  • Comparative Example 6 The difference between Comparative Example 6 and Comparative Example 3 is that in step 2, the negative electrode active material is graphite.
  • a lithium ion battery was prepared by the method of Comparative Example 1, and the capacity test and nail penetration test were performed.
  • the negative electrode active material is graphite.
  • Comparative Example 4 The method of Comparative Example 4 was used to prepare a lithium-ion battery and conduct a capacity test and a nail penetration test.
  • Comparative Example 8 The difference between Comparative Example 8 and Comparative Example 4 is that in step 2, the negative electrode active material is graphite.
  • Comparative Example 5 The method of Comparative Example 5 was used to prepare a lithium-ion battery and conduct a capacity test and a nail penetration test.
  • a lithium ion battery was prepared by the method of Comparative Example 1, and the capacity test and nail penetration test were performed.
  • the ratio of LiCoO 2 : Li 6 Mn 0.5 Ru 0.5 O 4 : PVDF:SP 86.5:3.5:5:5.
  • the negative electrode active material is graphite.
  • the lithium-ion battery to be tested is allowed to stand for 30 minutes in an environment of 25 ⁇ 3°C, and is charged to a voltage of 4.45V (rated voltage) at a rate of 0.05C (theoretical gram capacity of the positive electrode active material LiCoO 2 is 185mAh/g). ), then charge at a constant voltage to a current of 0.025C (cut-off current), after standing for 5 minutes, discharge at a constant current of 0.05C to a voltage of 3.0V, and record the specific discharge capacity and coulomb efficiency of the first cycle.
  • the lithium-ion battery to be tested is charged to a voltage of 4.45V (rated voltage) at a constant current rate of 0.05C (theoretical gram capacity of the positive electrode active material LiCoO 2 is 185mAh/g), and then charged to a current of 0.025C ( Cut-off current) to make the battery fully charged, and record the appearance of the battery before the test.
  • the battery is nail-pierced in an environment of 25 ⁇ 3°C.
  • the diameter of the steel nail is 4mm
  • the piercing speed is 30mm/s
  • the piercing positions are located at the shallow pit surface 15mm from the edge of the Al Tab cell and the distance from the Ni Tab cell.
  • the test will be conducted for 3.5 minutes or the surface temperature of the cell will be stopped after the temperature drops to 50°C. Take 10 cells as a group and observe the battery status during the test. The battery will not burn or explode as the judgment standard. Pass The rate is greater than or equal to 90% to pass the nail penetration test.
  • Table 1 shows the positive and negative electrode compositions and test results of Example 1 to Example 8 and Comparative Example 1 to Comparative Example 10.
  • the positive electrode in Comparative Example 1 and Comparative Example 2 did not add Li 5 FeO 4 , a positive electrode lithium supplement material.
  • the negative electrode active material of Comparative Example 3 to Comparative Example 5 is silicon oxide, and the corresponding positive electrode is respectively added with 1 wt%, 5 wt%, and 10 wt% of the positive electrode active material weight, Li 5 FeO 4 .
  • the negative electrode active material of Comparative Example 6 to Comparative Example 8 is graphite, and the corresponding positive electrode is respectively added with 1 wt%, 2 wt%, and 5 wt% of the positive electrode active material weight, Li 5 FeO 4 .
  • the positive electrode in Comparative Example 9 is added with Li 2 NiO 2 , which is a positive electrode lithium supplement material, which accounts for 10 wt% of the weight of the positive electrode active material, and the negative electrode active material is silicon oxide.
  • the positive electrode in Comparative Example 10 was added with Li 6 Mn 0.5 Ru 0.5 O 4 , a positive electrode lithium supplement material accounting for 4 wt% of the weight of the positive electrode active material, and the negative electrode active material was graphite.
  • the positive electrode lithium supplement material and the positive electrode active material were mixed and coated on the positive electrode current collector at one time.
  • Examples 1 to 8 all adopt a double-layer structure, that is, the positive electrode lithium supplement material layer is first coated, and then the positive electrode active material layer is coated.
  • the negative electrode active material is silicon oxide, and the Li 5 FeO 4 undercoated on the positive electrode accounts for about 1 wt%, 5 wt%, and 10 wt% of the weight of the positive electrode active material, respectively.
  • the negative electrode active material is graphite, and the Li 5 FeO 4 undercoated on the positive electrode accounts for about 1 wt%, 2 wt%, and 5 wt% of the weight of the positive electrode active material, respectively.
  • the negative electrode active material is silicon oxide, and the positive electrode is undercoated with Li 2 NiO 2 , which accounts for 10 wt% of the weight of the positive electrode active material.
  • the negative electrode active material is graphite, and the positive electrode is undercoated with Li 6 Mn 0.5 Ru 0.5 O 4 , which accounts for 4 wt% of the weight of the positive electrode active material.
  • the positive electrode lithium supplement material is not added (for example, Comparative Example 1 to Comparative Example 2), or the positive electrode lithium supplement material is directly mixed with the positive electrode active material and then coated (for example, , Comparative Example 3-Comparative Example 10) failed to pass the nail penetration experiment. This is mainly because the nail caused the internal short circuit of the battery during the nailing process, and the local temperature increased sharply. When the reaction temperature of the positive electrode active material is exceeded, it will cause a continuous chain reaction and release a large amount of heat, which eventually leads to the burning and burning of the battery. It may even explode when the degree is very severe.
  • Examples 1 to 8 can all pass the nail penetration test, and the pass rate is 100%. This is mainly because the positive electrode lithium-supplementing material layer coated on the current collector will generate a layer of delithiation products with stable properties and low electronic conductivity in situ during the first round of charging, which can effectively block the micro-short-circuit current when penetrating the nail. Conduction reduces the risk of thermal runaway and enhances the safety of lithium-ion batteries.
  • the positive electrode preparation method of the present application coats the positive electrode lithium supplement material layer and the positive electrode active material layer respectively, and by controlling the particle size of the positive electrode lithium supplement material and the thickness of the positive electrode lithium supplement material layer, the effect of the positive electrode lithium supplement material layer on the lithium ion battery is reduced.
  • the polarization effect. Li + needs to undergo slow solid phase diffusion in the bulk phase of the material to be released. The larger the particle size of the material, the longer the ion transmission path will be, which is very unfavorable for the removal of lithium from the positive electrode lithium supplement material.
  • This application micronizes the particles of the positive electrode lithium supplement material, shortens the solid phase diffusion distance, and reduces the polarization effect caused by too low ion conductivity.
  • the positive electrode lithium-supplementing material will generate poorly conductive products in situ after delithiation. If the positive electrode lithium-supplementing material layer is too thick, it will not be conducive to the transport of electrons. In this application, by controlling the thickness of the positive electrode lithium supplement layer, the positive electrode lithium supplement material layer is rolled to strengthen the contact between particles, which better overcomes the polarization effect caused by low electronic conductivity.
  • Comparative Example 3 to Comparative Example 5 and Example 1 to Example 3 adopt silicon oxide negative electrodes, and the addition amount of Li 5 FeO 4 as the positive electrode lithium supplement material accounts for about 1wt%, 5wt% and 10wt% of the weight of the positive electrode active material, respectively.
  • the charging capacity of LiCoO 2 is 188.5mAh/g
  • the first coulombic efficiency is 96%
  • the first lap delithiation capacity of the positive electrode replenishing material is 600mAh/g
  • the first efficiency is 0%.
  • the ideal addition amount of the positive electrode replenishing material Li 5 FeO 4 is about 4.96 wt% of the weight of the positive electrode active material (corresponding to Comparative Example 4 and Example 2).
  • Comparative Example 6 to Comparative Example 8 and Example 4 to Example 6 adopt graphite negative electrodes, and the addition amount of Li 5 FeO 4 as the positive electrode lithium supplement material is about 1wt%, 2wt% and 5wt% of the weight of the positive electrode active material. According to the above calculation, it can be known that the optimal addition amount of the positive electrode lithium supplement material is about 2.04wt% (corresponding to Comparative Example 7 and Example 5).
  • the lithium supplement effect is the best, and the reversible capacity and energy density of the lithium ion battery are increased the most.
  • the content of the positive electrode lithium supplement material is too small, the lithium source it provides is not enough to supplement the active lithium consumed by the SEI film; when the content of the positive electrode lithium supplement material is too high, the lithium source provided is far too much, and there is a part of lithium It will be embedded in the negative electrode active material during charging, but cannot be used during discharge, which is not good for increasing the energy density.
  • This application adopts a double-layer coating or deposition method, which can simultaneously realize the improvement of the energy density and safety of the lithium ion battery.
  • the application process is simple, easy to commercial production, and has great application prospects.
  • this application can also make appropriate changes and modifications to the above embodiments, such as selecting one or more of other lithium-rich oxide lithium-supplementing materials, or using deposition methods to obtain the positive electrode lithium-supplementing material layer. , Or choose other positive electrode active materials, binders and conductive agents. Therefore, this application is not limited to the specific implementations explained and described above, and some modifications and changes to this application should also fall within the protection scope of the claims of this application.
  • references to “some embodiments”, “partial embodiments”, “one embodiment”, “another example”, “examples”, “specific examples” or “partial examples” throughout the specification mean At least one embodiment or example in this application includes the specific feature, structure, material, or characteristic described in the embodiment or example. Therefore, descriptions appearing in various places throughout the specification, such as: “in some embodiments”, “in embodiments”, “in one embodiment”, “in another example”, “in an example “In”, “in a specific example” or “exemplary”, which are not necessarily quoting the same embodiment or example in this application.
  • the specific features, structures, materials, or characteristics herein can be combined in one or more embodiments or examples in any suitable manner.

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Abstract

正极补锂材料、包括正极补锂材料的正极及其制备方法。所述正极补锂材料包括Li 2M1O2、Li2M2O3、Li5FexM31-xO 4或Li6MnyM41-yO4中的至少一种，其中M1包含Ni、Mn、Cu、Fe、Cr或Mo中的至少一种；其中M2包含Ni、Mn、Fe、Mo、Zr、Si、Cu、Cr或Ru中的至少一种；其中M3包含Al、Nb、Co、Mn、Ni、Mo、Ru或Cr中的至少一种；其中M4包含Ni、Fe、Cu或Ru中的至少一种；其中0≤x≤1，0≤y≤1。提供了一种包括所述正极补锂材料的正极及其制备方法，可以有效地提高锂离子电池的能量密度并显著改善锂离子电池的穿钉安全性。

Description

正极补锂材料、包含正极补锂材料的正极及其制备方法 技术领域
本申请涉及储能技术领域，尤其涉及正极补锂材料、包含正极补锂材料的正极及其制备方法。
背景技术
相比于铅酸电池、镍镉电池和镍氢电池，锂离子电池具有能量密度高、功率密度大、工作电压高、循环性能好、寿命长、自放电低和温度适应范围宽等优点，自1991年商业化以来，已被广泛应用于3C数码领域。然而，随着智能手机和电动汽车的蓬勃发展，现有的锂离子电池的能量密度和循环寿命越来越无法满足市场的需求。
锂离子电池的能量密度和循环寿命与其首次库伦效率和负极固体电解质界面(SEI)膜的形成密切相关，在锂离子电池的首次充电过程中，负极表面形成的SEI膜会将大量的活性锂转化成碳酸锂、氟化锂和烷基锂，从而造成正极材料的锂损失。在使用石墨作为负极的锂离子电池体系中，首次充电会消耗约10％的锂源；当采用高比容量的负极材料，例如合金类(硅、锡等)、氧化物类(氧化硅、氧化锡)和无定形碳等作为负极时，正极锂源的消耗将进一步加剧。
对正极或负极进行预补锂是提升锂离子电池的能量密度的一种行之有效的方法。已经有研究表明可以通过引入活性较高的金属锂或金属锂盐来补偿锂离子电池在首次充放电时的容量损失。然而，现有的补锂材料主要涉及稳定化的金属锂粉或有机锂盐，其活性依然过高，无法长时间稳定保存，增加了操作难度和生产风险。此外，现有的补锂材料与现有的溶剂和粘结剂也存在着兼容性问题，如稳定化的锂金属粉末会与常见的调浆溶剂N-甲基吡咯烷酮(NMP)反应。
正极补锂材料的电势高，与现有的锂离子电池的加工工艺兼容性好，更加安全和便于操作，因此得到了学术界和产业界越来越多的关注。然而，现有的正极补锂材料(如L-抗坏血酸锂、D-异抗坏血酸锂、焦亚硫酸锂，亚硫酸锂和植酸锂等)在空气中很容易被氧化，且难以大批量合成，不利于大规模工业生产。
发明内容
本申请提供一种正极补锂材料、包含正极补锂材料的正极及其制备方法以试图在至少某种程度上解决至少一个存在于相关领域中的问题。
根据本申请的实施例，本申请提供了一种正极补锂材料，其包括Li 2M1O 2、Li 2M2O 3、Li 5Fe xM3 1-xO 4或Li 6Mn yM4 1-yO 4中的至少一种，其中M1包含Ni、Mn、Cu、Fe、Cr或Mo中的至少一种；其中M2包含Ni、Mn、Fe、Mo、Zr、Si、Cu、Cr或Ru中的至少一种；其中M3包含Al、Nb、Co、Mn、Ni、Mo、Ru或Cr中的至少一种；其中M4包含Ni、Fe、Cu或Ru中的至少一种；其中0≤x≤1，0≤y≤1。
根据本申请的实施例，正极补锂材料的首次脱锂容量大于等于约300mAh/g。
根据本申请的实施例，正极补锂材料的中值粒径D50小于等于约1.5μm。
根据本申请的实施例，正极补锂材料包括Li 2NiO 2、Li 2MoO 3、Li 5FeO 4、Li 5Fe 0.9Al 0.1O 4、Li 6MnO 4或Li 6Mn 0.5Ru 0.5O 4中的至少一种。
根据本申请的实施例，本申请还提供了一种正极，所述正极包括正极补锂材料层，所述正极补锂材料层包含上述任意一种正极补锂材料。
根据本申请的实施例，正极补锂材料层的厚度小于等于约10μm。
根据本申请的实施例，正极补锂材料层还包含导电剂和粘结剂，其中粘结剂包括聚丙烯、聚乙烯、聚偏氟乙烯、偏氟乙烯-六氟丙烯、聚四氟乙烯或聚六氟丙烯中的至少一种，其中导电剂包括导电碳黑、碳纤维、乙炔黑、科琴黑、石墨烯或碳纳米管中的至少一种。
根据本申请的实施例，以正极补锂材料层的总重量计，正极补锂材料的重量百分比为约80wt％-约90wt％，粘结剂的重量百分比为约5wt％-约10wt％，导电剂的重量百分比为约5wt％-约10wt％。
根据本申请的实施例，正极还包括正极活性材料层，其中正极补锂材料层布置在集流体上，正极活性材料层布置在正极补锂材料层上。
根据本申请的实施例，正极活性材料层包含正极活性材料、粘结剂和导电剂，其中正极活性材料包括钴酸锂、磷酸铁锂、磷酸锰铁锂、磷酸钒锂、磷酸钒氧锂、钒酸锂、锰酸锂、镍酸锂、镍钴锰酸锂、富锂锰基材料或镍钴铝酸锂中的至少一种，其中粘结剂 包括含氟树脂、聚丙烯树脂、纤维型粘结剂、橡胶型粘结剂或聚酰亚胺型粘结剂中的至少一种，其中导电剂包括导电碳黑，碳纤维，乙炔黑，科琴黑，石墨烯或碳纳米管中的至少一种。
根据本申请的实施例，以正极活性材料层的总重量计，正极活性材料的重量百分比为约80wt-约98wt％，粘结剂的重量百分比为约0.5wt％-约10wt％，导电剂的重量百分比为约0.5wt％-约10wt％。
根据本申请的实施例，正极补锂材料层中的正极补锂材料占正极活性材料层中的正极活性材料的约1wt％-约10wt％。
根据本申请的实施例，本申请还提供了一种正极的制备方法，所述方法包括：将上述任意一种正极补锂材料沉积或涂布在集流体上；及将沉积或涂布有正极补锂材料的集流体干燥，然后涂布正极活性材料。
根据本申请的实施例，本申请还提供了一种电化学装置，其包括上述任意一种正极或由上述方法制备得到的正极。
根据本申请的实施例，本申请还提供了一种电子装置，其包括上述任意一种电化学装置。
本申请实施例的额外层面及优点将部分地在后续说明中描述、显示、或是经由本申请实施例的实施而阐释。
具体实施方式
本申请的实施例将会被详细的描示在下文中。在此所描述的实施例为说明性质的且用于提供对本申请的基本理解。本申请的实施例不应该被解释为对本申请的限制。
如本文中所使用，术语“大致”、“大体上”、“实质”及“约”用以描述及说明小的变化。当与事件或情形结合使用时，所述术语可指代其中事件或情形精确发生的例子以及其中事件或情形极近似地发生的例子。举例来说，当结合数值使用时，术语可指代小于或等于所述数值的±10％的变化范围，例如小于或等于±5％、小于或等于±4％、小于或等于±3％、小于或等于±2％、小于或等于±1％、小于或等于±0.5％、小于或等于±0.1％、或小于或等于±0.05％。举例来说，如果两个数值之间的差值小于或等于所述值的平均值的±10％(例如小于或等于±5％、小于或等于±4％、小于或等于±3％、 小于或等于±2％、小于或等于±1％、小于或等于±0.5％、小于或等于±0.1％、或小于或等于±0.05％)，那么可认为所述两个数值“大体上”相同。
另外，有时在本文中以范围格式呈现量、比率和其它数值。应理解，此类范围格式是用于便利及简洁起见，且应灵活地理解，不仅包含明确地指定为范围限制的数值，而且包含涵盖于所述范围内的所有个别数值或子范围，如同明确地指定每一数值及子范围一般。
在具体实施方式及权利要求书中，由术语“中的至少一者”、“中的至少一个”、“中的至少一种”或其他相似术语所连接的项目的列表可意味着所列项目的任何组合。例如，如果列出项目A及B，那么短语“A及B中的至少一者”意味着仅A；仅B；或A及B。在另一实例中，如果列出项目A、B及C，那么短语“A、B及C中的至少一者”意味着仅A；或仅B；仅C；A及B(排除C)；A及C(排除B)；B及C(排除A)；或A、B及C的全部。项目A可包含单个元件或多个元件。项目B可包含单个元件或多个元件。项目C可包含单个元件或多个元件。
本申请提供一种正极补锂材料、包括正极补锂材料的正极及其制备方法，并且还提供了包括所述正极的电化学装置和电子装置。
一、正极补锂材料
本申请提供了一种正极补锂材料，其包括Li 2M1O 2、Li 2M2O 3、Li 5Fe xM3 1-xO 4或Li 6Mn yM4 1-yO 4中的至少一种，其中M1包含Ni、Mn、Cu、Fe、Cr或Mo中的至少一种；其中M2包含Ni、Mn、Fe、Mo、Zr、Si、Cu、Cr或Ru中的至少一种；其中M3包含Al、Nb、Co、Mn、Ni、Mo、Ru或Cr中的至少一种；其中M4包含Ni、Fe、Cu或Ru中的至少一种；其中0≤x≤1，0≤y≤1。
在一些实施例中，正极补锂材料包括Li 2NiO 2、Li 2MoO 3、Li 5FeO 4、Li 5Fe 0.9Al 0.1O 4、Li 6MnO 4或Li 6Mn 0.5Ru 0.5O 4中的至少一种。在一些实施例中，正极补锂材料包括Li 5FeO 4。在一些实施例中，正极补锂材料包括Li 2NiO 2。在一些实施例中，正极补锂材料包括Li 6Mn 0.5Ru 0.5O 4。
在一些实施例中，正极补锂材料的首次脱锂容量大于等于约300mAh/g。在一些实施例中，正极补锂材料的首次脱锂容量大于等于约350mAh/g、大于等于约400mAh/g、大于等于约500mAh/g或大于等于约600mAh/g。在一些实施例中，正极补锂材料的首次脱锂容量为约300mAh/g-约350mAh/g、约300mAh/g-约400mAh/g、约300mAh/g-约 500mAh/g或约300mAh/g-约600mAh/g等。
在一些实施例中，正极补锂材料的中值粒径D50小于等于约1.5μm。在一些实施例中，正极补锂材料的中值粒径D50小于等于约1.2μm、小于等于约1μm或小于等于约0.5μm。在一些实施例中，正极补锂材料的中值粒径D50为约0.5μm-约1.5μm、约1μm-约1.5μm、约0.1μm-约1.5μm等。
二、正极
本申请提供了一种正极，其包括正极补锂材料层，所述正极补锂材料层包含上述任意一种正极补锂材料。
在一些实施例中，以正极补锂材料层的总重量计，正极补锂材料的重量百分比为约80wt％-约90wt％。在一些实施例中，以正极补锂材料层的总重量计，正极补锂材料的重量百分比为约80wt％-约85wt％、约80wt％-约90wt％或约85wt％-约90wt％等。
在一些实施例中，正极补锂材料层的厚度小于等于约10μm。在一些实施例中，正极补锂材料层的厚度小于等于约5μm、小于等于约3nm或小于等于约1nm。在一些实施例中，正极补锂材料层的厚度为约5μm-约10μm、约1μm-约5μm、约1μm-约10μm或约3μm-约10μm等。
在一些实施例中，正极补锂材料层还包含粘结剂。在一些实施例中，粘结剂包括聚丙烯、聚乙烯、聚偏氟乙烯(PVDF)、偏氟乙烯-六氟丙烯、聚四氟乙烯或聚六氟丙烯中的至少一种。在一些实施例中，正极补锂材料层中的粘结剂包括聚偏氟乙烯。
在一些实施例中，以正极补锂材料层的总重量计，粘结剂的重量百分比为约5wt％-约10wt％。在一些实施例中，以正极补锂材料层的总重量计，粘结剂的重量百分比为约5wt％-约7wt％或约7wt％-约10wt％等。
在一些实施例中，正极补锂材料层还包含导电剂。在一些实施例中，导电剂包括导电碳黑(SP)、碳纤维、乙炔黑、科琴黑、石墨烯或碳纳米管(CNT)中的至少一种。在一些实施例中，正极补锂材料层中的导电剂包括碳纳米管。
在一些实施例中，以正极补锂材料层的总重量计，导电剂的重量百分比为约5wt％-约10wt％。在一些实施例中，以正极补锂材料层的总重量计，导电剂的重量百分比为约5wt％-约7wt％或约7wt％-约10wt％等。
在一些实施例中，正极还包括正极活性材料层，其中正极补锂材料层布置在集流体 上，正极活性材料层布置在正极补锂材料层上。在一些实施例中，集流体可以是铝(Al)，但其不限于此。
在一些实施例中，所述正极活性材料层包含正极活性材料、粘结剂和导电剂。在一些实施例中，正极活性材料包括钴酸锂(LiCoO 2)、磷酸铁锂、磷酸锰铁锂、磷酸钒锂、磷酸钒氧锂、钒酸锂、锰酸锂、镍酸锂、镍钴锰酸锂、富锂锰基材料或镍钴铝酸锂中的至少一种。在一些实施例中，正极活性材料包括截止电压大于等于约4.45V的钴酸锂。
在一些实施例中，正极活性材料层中的粘结剂包括含氟树脂、聚丙烯树脂、纤维型粘结剂、橡胶型粘结剂或聚酰亚胺型粘结剂中的至少一种。在一些实施例中，正极活性材料层中的粘结剂包括聚偏氟乙烯。
在一些实施例中，正极活性材料层中的导电剂包括导电碳黑，碳纤维，乙炔黑，科琴黑，石墨烯或碳纳米管中的至少一种。在一些实施例中，正极活性材料层中的导电剂包括导电碳黑。
在一些实施例中，以正极活性材料层的总重量计，正极活性材料的重量百分比为约80wt-约98wt％。在一些实施例中，以正极活性材料层的总重量计，正极活性材料的重量百分比为约80wt-约85wt％、约80wt-约90wt％、约85wt-约95wt％或约85wt-约98wt％等。
在一些实施例中，以正极活性材料层的总重量计，粘结剂的重量百分比为约0.5wt％-约10wt％。在一些实施例中，以正极活性材料层的总重量计，粘结剂的重量百分比为约0.5wt％-约5wt％、约1wt％-约5wt％、约5wt％-约10wt％或约1wt％-约10wt％等。
在一些实施例中，以正极活性材料层的总重量计，导电剂的重量百分比为约0.5wt％-约10wt％。在一些实施例中，以正极活性材料层的总重量计，导电剂的重量百分比为约0.5wt％-约5wt％、约1wt％-约5wt％、约5wt％-约10wt％或约1wt％-约10wt％等。
在一些实施例中，正极补锂材料层中的正极补锂材料占正极活性材料层中的正极活性材料的约1wt％-约10wt％。在一些实施例中，正极补锂材料层中的正极补锂材料占正极活性材料层中的正极活性材料的约约1wt％-约2wt％、约1wt％-约5wt％、约2wt％-约5wt％或约5wt％-约10wt％等。
三、正极的制备方法
本申请还提供了一种正极的制备方法，所述方法包括将本申请的正极补锂材料沉积 或涂布在集流体上；及将沉积或涂布有正极补锂材料的集流体干燥，然后涂布正极活性材料，以制备上述正极。
本申请的制备方法将正极补锂材料层底涂(涂布或沉积)在集流体上，并严格控制正极补锂材料的粒度和正极补锂材料层的厚度，以减小正极补锂材料层的极化。一方面，在首圈充电时，正极补锂材料完成全部脱锂，释放出锂离子补充负极SEI膜所消耗的活性锂，提升了电化学装置的可逆容量和能量密度。另一方面，正极补锂材料脱锂后留下导电性较差的脱锂产物覆盖在集流体上，能够在很大程度上减少穿钉带来的微短路风险，提高了电化学装置(特别是高能量密度的锂离子电池)的安全性。
本申请采用双层涂布或沉积的方法，可同时实现电化学装置的能量密度和安全性的提升。本申请的正极补锂材料的脱锂产物结构稳定，首圈脱锂后在集流体上原位形成的隔离层能极大减小电池穿钉失效的风险。此外，本申请的正极制备方法简单，易于商业化生产。
四、电化学装置
本申请的电化学装置包括本申请的上述任意一种正极。本申请的电化学装置可以包括发生电化学反应的任何装置，它的具体实例包括所有种类的一次电池、二次电池、燃料电池、太阳能电池或电容。特别地，该电化学装置是锂二次电池，包括锂金属二次电池、锂离子二次电池、锂聚合物二次电池或锂离子聚合物二次电池。在一些实施例中，本申请的电化学装置包括本申请的正极、负极、置于正极和负极之间的隔离膜以及电解液。在一些实施例中，电化学装置为锂离子电池。
在一些实施例中，负极包括负极集流体和位于负极集流体上的负极活性材料层。负极活性材料包括可逆地嵌入/脱嵌锂离子的材料。在一些实施例中，可逆地嵌入/脱嵌锂离子的材料包括碳材料。在一些实施例中，碳材料可以是在锂离子可充电电池中通常使用的任何基于碳的负极活性材料。在一些实施例中，碳材料包括，但不限于：结晶碳、非晶碳或它们的混合物。结晶碳可以是无定形的、片形的、小片形的、球形的或纤维状的天然石墨或人造石墨。非晶碳可以是软碳、硬碳、中间相沥青碳化物、煅烧焦等。
在一些实施例中，负极活性材料包括，但不限于：锂金属、结构化的锂金属、天然石墨、人造石墨、中间相微碳球(MCMB)、硬碳、软碳、硅、氧化硅(SiO x)、硅-碳复合物、Li-Sn合金、Li-Sn-O合金、Sn、SnO、SnO 2、尖晶石结构的锂化TiO 2-Li 4Ti 5O 12、Li-Al合金或其任意组合。
当负极包括硅碳化合物时，基于负极活性材料总重量，硅∶碳＝约1∶10～10∶1，硅碳化合物的中值粒径D50为约0.1μm-100μm。当负极包括合金材料时，可使用蒸镀法、溅射法、镀敷法等方法形成负极活性物质层。当负极包括锂金属时，例如用具有球形绞状的导电骨架和分散在导电骨架中的金属颗粒形成负极活性物质层。在一些实施例中，球形绞状的导电骨架可具有约5％-约85％的孔隙率。在一些实施例中，锂金属负极活性物质层上还可设置保护层。
在一些实施例中，负极还可以包括粘合剂。粘合剂提高负极活性材料颗粒彼此间的结合和负极活性材料与负极集流体的结合。在一些实施例中，粘合剂包括，但不限于：聚乙烯醇、羧甲基纤维素、羟丙基纤维素、二乙酰基纤维素、聚氯乙烯、羧化的聚氯乙烯、聚氟乙烯、含亚乙基氧的聚合物、聚乙烯吡咯烷酮、聚氨酯、聚四氟乙烯、聚偏1，1-二氟乙烯、聚乙烯、聚丙烯、聚丙烯酸(PAA)、丁苯橡胶、丙烯酸(酯)化的丁苯橡胶、环氧树脂、尼龙等。
在一些实施例中，负极还可以导电剂。导电剂包括，但不限于：基于碳的材料、基于金属的材料、导电聚合物或它们的混合物。在一些实施例中，基于碳的材料选自天然石墨、人造石墨、导电碳黑、乙炔黑、科琴黑、碳纤维或其任意组合。在一些实施例中，基于金属的材料选自金属粉、金属纤维、铜、镍、铝、银。在一些实施例中，导电聚合物为聚亚苯基衍生物。
在一些实施例中，负极集流体包括，但不限于：铜(Cu)箔、镍箔、不锈钢箔、钛箔、泡沫镍、泡沫铜、覆有导电金属的聚合物基底和它们的任意组合。
负极可以通过本领域公知的制备方法制备。例如，负极可以通过如下方法获得：在溶剂中将活性材料、导电材料和粘合剂混合，以制备活性材料组合物，并将该活性材料组合物涂覆在集流体上。在一些实施例中，溶剂可以包括水等，但不限于此。
在一些实施例中，隔离膜包括，但不限于，选自聚乙烯、聚丙烯、聚对苯二甲酸乙二醇酯、聚酰亚胺和芳纶中的至少一种。举例来说，聚乙烯包括选自高密度聚乙烯、低密度聚乙烯和超高分子量聚乙烯中的至少一种组分。尤其是聚乙烯和聚丙烯，它们对防止短路具有良好的作用，并可以通过关断效应改善锂离子电池的稳定性。
在一些实施例中，电解质可以是凝胶电解质、固态电解质和电解液中的一种或多种，电解液包括锂盐和非水溶剂。
在一些实施例中，锂盐可以选自LiPF 6、LiBF 4、LiAsF 6、LiClO 4、LiB(C 6H 5) 4、LiCH 3SO 3、 LiCF 3SO 3、LiN(SO 2CF 3) 2、LiC(SO 2CF 3) 3、LiSiF 6、LiBOB或者二氟硼酸锂中的一种或多种。例如，锂盐选用LiPF 6，因为它可以给出高的离子导电率并改善循环特性。
在一些实施例中，非水溶剂可为碳酸酯化合物、羧酸酯化合物、醚化合物、其它有机溶剂或它们的组合。
在一些实施例中，碳酸酯化合物可为链状碳酸酯化合物、环状碳酸酯化合物、氟代碳酸酯化合物或其组合。
在一些实施例中，链状碳酸酯化合物的实例为碳酸二乙酯(DEC)、碳酸二甲酯(DMC)、碳酸二丙酯(DPC)、碳酸甲丙酯(MPC)、碳酸乙丙酯(EPC)、碳酸甲乙酯(MEC)及其组合。所述环状碳酸酯化合物的实例为碳酸亚乙酯(EC)、碳酸亚丙酯(PC)、碳酸亚丁酯(BC)、碳酸乙烯基亚乙酯(VEC)或者其组合。所述氟代碳酸酯化合物的实例为碳酸氟代亚乙酯(FEC)、碳酸1，2-二氟亚乙酯、碳酸1，1-二氟亚乙酯、碳酸1，1，2-三氟亚乙酯、碳酸1，1，2，2-四氟亚乙酯、碳酸1-氟-2-甲基亚乙酯、碳酸1-氟-1-甲基亚乙酯、碳酸1，2-二氟-1-甲基亚乙酯、碳酸1，1，2-三氟-2-甲基亚乙酯、碳酸三氟甲基亚乙酯或者其组合。
在一些实施例中，羧酸酯化合物的实例为乙酸甲酯、乙酸乙酯、乙酸正丙酯、乙酸叔丁酯、丙酸甲酯、丙酸乙酯、丙酸丙酯、γ-丁内酯、癸内酯、戊内酯、甲瓦龙酸内酯、己内酯、甲酸甲酯或者其组合。
在一些实施例中，醚化合物的实例为二丁醚、四甘醇二甲醚、二甘醇二甲醚、1，2-二甲氧基乙烷、1，2-二乙氧基乙烷、乙氧基甲氧基乙烷、2-甲基四氢呋喃、四氢呋喃或者其组合。
在一些实施例中，其它有机溶剂的实例为二甲亚砜、1，2-二氧戊环、环丁砜、甲基环丁砜、1，3-二甲基-2-咪唑烷酮、N-甲基-2-吡咯烷酮、甲酰胺、二甲基甲酰胺、乙腈、磷酸三甲酯、磷酸三乙酯、磷酸三辛酯、磷酸酯或者其组合。
五、应用
由本申请所述的正极制造的电化学装置适用于各种领域的电子装置。
本申请的电化学装置的用途没有特别限定，其可用于现有技术中已知的任何用途。在一个实施例中，本申请的电化学装置可用于，但不限于，笔记本电脑、笔输入型计算机、移动电脑、电子书播放器、便携式电话、便携式传真机、便携式复印机、便携式打 印机、头戴式立体声耳机、录像机、液晶电视、手提式清洁器、便携CD机、迷你光盘、收发机、电子记事本、计算器、存储卡、便携式录音机、收音机、备用电源、电机、汽车、摩托车、助力自行车、自行车、照明器具、玩具、游戏机、钟表、电动工具、闪光灯、照相机、家庭用大型蓄电池和锂离子电容器等。
六、实施例
以下，举出实施例和对比例对本申请进一步具体地进行说明，但只要不脱离其主旨，则本申请并不限定于这些实施例。
实施例1
步骤一，以LiCoO 2∶PVDF∶SP＝90∶5∶5的重量比例将其溶于NMP中，搅拌均匀后得到正极活性材料层浆料。
步骤二，以Li 5FeO 4∶PVDF∶CNT＝90∶5∶5的重量比例将其溶于NMP中，搅拌均匀后得到正极补锂材料层浆料，其中Li 5FeO 4的中值粒径D50为1.5μm，其约占正极活性材料层中的LiCoO 2重量的1％。
步骤三，先将正极补锂材料层浆料喷涂在Al集流体表面，烘干辊压，控制其厚度为5μm，再将正极活性材料层浆料涂布在正极补锂材料层上，干燥后得到双层结构的补锂正极极片。
步骤四，以SiO x(0.5＜x＜1.6)∶PAA∶SP＝90∶5∶5的重量比例将其溶于去离子水中，搅拌均匀后得到负极浆料，将其涂布在Cu集流体表面，干燥后得到负极极片。
步骤五，将上述制备的正负极极片经过辊压，裁切，叠片，注液和封装，得到软包锂离子电池。
对锂离子电池进行容量测试和穿钉测试。
实施例2
用实施例1的方法制备锂离子电池并进行容量测试和穿钉测试。
实施例2与实施例1的不同之处在于：步骤二中的比例为Li 5FeO 4∶PVDF∶CNT＝80∶10∶10，Li 5FeO 4约占正极活性材料层中LiCoO 2重量的5％；步骤三中控制正极补锂材料层的厚度为7μm。
实施例3
用实施例1的方法制备锂离子电池并进行容量测试和穿钉测试。
实施例3与实施例1的不同之处在于：步骤二中Li 5FeO 4约占正极活性材料层中LiCoO 2重量的10％；步骤三中控制正极补锂材料层的厚度为10μm。
实施例4
用实施例1的方法制备锂离子电池并进行容量测试和穿钉测试。
实施例4与实施例1的不同之处在于：步骤四中负极活性材料为石墨。
实施例5
用实施例2的方法制备锂离子电池并进行容量测试和穿钉测试。
实施例5与实施例2的不同之处在于：步骤二中Li 5FeO 4约占正极活性材料层中LiCoO 2重量的2％；步骤四中负极活性材料为石墨。
实施例6
用实施例3的方法制备锂离子电池并进行容量测试和穿钉测试。
实施例6与实施例3的不同之处在于：步骤二中Li 5FeO 4约占正极活性材料层中LiCoO 2重量的5％；步骤四中负极活性材料为石墨。
实施例7
用实施例1的方法制备锂离子电池并进行容量测试和穿钉测试。
实施例7与实施例1的不同之处在于：步骤二中补锂材料为Li 2NiO 2，且Li 2NiO 2的中值粒径D50为1.0μm，其约占正极活性材料层中的LiCoO 2重量的10％。
实施例8
用实施例1的方法制备锂离子电池并进行容量测试和穿钉测试。
实施例8与实施例1的不同之处在于：步骤二中补锂材料为Li 6Mn 0.5Ru 0.5O 4，且Li 6Mn 0.5Ru 0.5O 4的中值粒径D50为1.2μm，其约占正极活性材料层中的LiCoO 2重量的4％，步骤四中负极活性材料为石墨。
对比例1
步骤一，以LiCoO 2∶PVDF∶SP＝90∶5∶5的重量比例将其溶于NMP中，搅拌均匀后得到正极活性材料层浆料，将其涂布在Al集流体表面，干燥后得到正极极片。
步骤二，以SiO x(0.5＜x＜1.6)∶PAA∶SP＝90∶5∶5的重量比例将其溶于去离子水中，搅拌均匀后得到负极浆料，将其涂布在Cu集流体表面，干燥后得到负极极片。
步骤三，将上述正负极极片经过辊压，裁切，叠片，注液和封装，得到软包锂离子电池。
对锂离子电池进行容量测试和穿钉测试。
对比例2
用对比例1的方法制备锂离子电池并进行容量测试和穿钉测试。
对比例2与对比例1的不同之处在于：步骤二中负极活性材料为石墨。
对比例3
用对比例1的方法制备锂离子电池并进行容量测试和穿钉测试。
对比例3与对比例1的不同之处在于：按LiCoO 2∶Li 5FeO 4＝100∶1的比例将其混合后一次涂布，即在步骤一中各组分的配比为LiCoO 2∶Li 5FeO 4∶PVDF∶SP＝89.1∶0.9∶5∶5。
对比例4
用对比例1的方法制备锂离子电池并进行容量测试和穿钉测试。
对比例4与对比例1的不同之处在于：按LiCoO 2∶Li 5FeO 4＝100∶5的比例将其混合后一次涂布，即在步骤一中各组分的配比为LiCoO 2∶Li 5FeO 4∶PVDF∶SP＝85.7∶4.3∶5∶5。
对比例5
用对比例1的方法制备锂离子电池并进行容量测试和穿钉测试。
对比例5与对比例1的不同之处在于：对比例5按LiCoO 2∶Li 5FeO 4＝100∶10的比例将其混合后一次涂布，即在步骤一中各组分的配比为LiCoO 2∶Li 5FeO 4∶PVDF∶SP＝81.8∶8.2∶5∶5。
对比例6
用对比例3的方法制备锂离子电池并进行容量测试和穿钉测试。
对比例6与对比例3的不同之处在于：步骤二中负极活性材料为石墨。
对比例7
用对比例1的方法制备锂离子电池并进行容量测试和穿钉测试。
对比例7与对比例1的不同之处在于：按LiCoO 2∶Li 5FeO 4＝100∶2的比例将其混合后一次涂布，即在步骤一中各组分的配比为LiCoO 2∶Li 5FeO 4∶PVDF∶SP＝88.2∶1.8∶5∶5。
步骤二中负极活性材料为石墨。
对比例8
用对比例4的方法制备锂离子电池并进行容量测试和穿钉测试。
对比例8与对比例4的不同之处在于：步骤二中负极活性材料为石墨。
对比例9
用对比例5的方法制备锂离子电池并进行容量测试和穿钉测试。
对比例9与对比例5的不同之处在于：对比例9按LiCoO 2∶Li 2NiO 2＝100∶10的比例将其混合后一次涂布，即在步骤一中各组分的配比为LiCoO 2∶Li 2NiO 2∶PVDF∶SP＝81.8∶8.2∶5∶5。
对比例10
用对比例1的方法制备锂离子电池并进行容量测试和穿钉测试。
对比例10与对比例1的不同之处在于：对比例10按LiCoO 2∶Li 6Mn 0.5Ru 0.5O 4＝100∶4的比例将其混合后一次涂布，即在步骤一中各组分的配比为LiCoO 2∶Li 6Mn 0.5Ru 0.5O 4∶PVDF∶SP＝86.5∶3.5∶5∶5。
步骤二中负极活性材料为石墨。
七、测试方法及测试结果
容量测试
将待测的锂离子电池在25±3℃环境中静置30分钟，以0.05C(正极活性材料LiCoO 2理论克容量以185mAh/g计)的倍率恒流充电至电压为4.45V(额定电压)，随后恒压充电至电流为0.025C(截止电流)，静置5分钟后，以0.05C的倍率恒流放电至电压为3.0V，纪录首圈放电比容量和库伦效率。
放电比容量＝放电容量/正极活性物质(钴酸锂)重量。
穿钉测试
将待测的锂离子电池以0.05C(正极活性材料LiCoO 2理论克容量以185mAh/g计) 的倍率恒流充电至电压为4.45V(额定电压)，随后恒压充电至电流为0.025C(截止电流)，使电池达到满充状态，记录测试前电池外观。在25±3℃环境中对电池进行穿钉测试，钢钉直径4mm，穿刺速度30mm/s，穿钉位置分别位于浅坑面距离Al Tab(极耳)电芯边缘15mm处和距离Ni Tab电芯边缘15mm处，测试进行3.5min或电芯表面温度降到50℃以后停止测试，以10个电芯为一组，观察测试过程中电池状态，以电池不燃烧，不爆炸为判定标准，通过率大于等于90％算通过穿钉测试。
表1示出了实施例1-实施例8以及对比例1-对比例10的正负极组成及测试结果。
表1
Figure PCTCN2019122055-appb-000001
对比例1和对比例2中的正极未添加正极补锂材料Li 5FeO 4。对比例3至对比例5的负极活性材料为氧化硅，并且对应的正极中分别添加了占正极活性材料重量的1wt％、 5wt％、10wt％的正极补锂材料Li 5FeO 4。对比例6至对比例8的负极活性材料为石墨，并且对应的正极中分别添加了占正极活性材料重量的1wt％、2wt％、5wt％的正极补锂材料Li 5FeO 4。对比例9中的正极添加了占正极活性材料重量10wt％的正极补锂材料Li 2NiO 2，负极活性材料为氧化硅。对比例10中的正极添加了占正极活性材料重量4wt％的正极补锂材料Li 6Mn 0.5Ru 0.5O 4，负极活性材料为石墨。对比例3至对比例10将正极补锂材料和正极活性材料混合后一次涂布在正极集流体上。
实施例1至实施例8均采用了双层结构，即先底涂正极补锂材料层，再涂布正极活性材料层。在实施例1至实施例3中，负极活性材料为氧化硅，正极底涂的Li 5FeO 4分别约占正极活性材料重量的1wt％、5wt％、10wt％。在实施例4至实施例6中，负极活性材料为石墨，正极底涂的Li 5FeO 4分别约占正极活性材料重量的1wt％、2wt％、5wt％。实施例7中，负极活性材料为氧化硅，正极底涂Li 2NiO 2，其占正极活性材料重量的10wt％。实施例8中，负极活性材料为石墨，正极底涂Li 6Mn 0.5Ru 0.5O 4，其占正极活性材料重量的4wt％。
如表1所示，比较穿钉测试结果可以得知，不添加正极补锂材料(例如对比例1至对比例2)，或者将正极补锂材料直接与正极活性材料混合后一次涂布(例如，对比例3-对比例10)无法通过穿钉实验。这主要是由于穿钉过程中钉子引起了电池内部短路，局部温度剧烈上升，当超过正极活性材料的反应温度后，会引起持续性连锁反应，放出大量的热量，最终导致了电池的燃烧，燃烧程度非常剧烈时甚至会出现爆炸。
与之相对，采用双层结构的实施的穿钉性能均得到了极大的改善，实施例1-实施例8均可通过穿钉测试，通过率为100％。这主要是因为涂覆在集流体上的正极补锂材料层在首圈充电时会原位生成一层性质稳定，电子电导很低的脱锂产物，在穿钉时能有效阻挡微短路电流的传导，降低了热失控的风险，增强了锂离子电池的安全性。
本申请的正极制备方法分别涂布正极补锂材料层和正极活性材料层，并且通过控制正极补锂材料的粒度和正极补锂材料层的厚度，减小了正极补锂材料层对锂离子电池的极化影响。Li +在材料体相需经过缓慢的固相扩散才可脱出，材料颗粒尺寸越大，离子传输路径就会越长，对于正极补锂材料脱锂非常不利。本申请将正极补锂材料的颗粒微纳化，缩短了固相扩散距离，减小了离子电导过低带来的极化影响。另一方面，正极补锂材料脱锂后会原位生成导电性很差的产物，正极补锂材料层太厚会不利于电子的输运。本申请通过控制正极补锂层的厚度，对正极补锂材料层进行辊压加强颗粒间接触，较好的克服了电子电导低带来的极化影响。
比较对比例3和实施例1、对比例4和实施例2、对比例5和实施例3、对比例6和实施例4、对比例7和实施例5、对比例8和实施例6、对比例9和实施例7以及对比例10和实施例8可知，在首圈充电时，正极补锂材料脱锂容量几乎相同。
比较对比例3至对比例10、实施例1至实施例8与对比例1至对比例2可知，无论是混合后一次涂布还是双层结构涂布，只要加入了正极补锂材料，锂离子电池的放电比容量均得到了很大提升，这主要是因为正极补锂材料在充电时释放出的锂离子可以在很大程度上补充负极SEI膜所消耗的活性锂，进而提升了锂离子电池的可逆容量和能量密度。
对比例3至对比例5和实施例1至实施例3采用氧化硅负极，其正极补锂材料Li 5FeO 4的添加量分别约占正极活性材料重量的1wt％、5wt％和10wt％，按照LiCoO 2充电容量188.5mAh/g，首次库伦效率96％，正极补锂材料首圈脱锂容量600mAh/g，首效为0％来计算，正极补锂材料Li 5FeO 4的理想添加量约为正极活性材料重量的4.96wt％(对应于对比例4和实施例2)。
同理，对比例6至对比例8和实施例4至实施例6采用石墨负极，其正极补锂材料Li 5FeO 4的添加量分别约占正极活性材料重量的1wt％、2wt％和5wt％，按照上述计算可知，正极补锂材料的最佳添加量约为2.04wt％(对应于对比例7和实施例5)。
以最佳百分比添加正极补锂材料时，补锂效果最好，对锂离子电池的可逆容量和能量密度提升最大。当正极补锂材料的含量过少时，其提供的锂源不足以补充SEI膜所消耗的活性锂；当正极补锂材料的含量过高时，其所提供的锂源远远过量，有一部分锂会在充电时嵌入负极活性材料，而放电时无法利用，对提升能量密度不利。
本申请采用双层涂布或沉积的方法，可同时实现锂离子电池的能量密度和安全性的提升。本申请工艺简单，易于商业化生产，具有较大的应用前景。
根据上述原理，本申请还可以对上述实施方式进行适当的变更和修改，如选用其它的富锂氧化物补锂材料中的一种或几种，或改用沉积的方式得到正极补锂材料层，或选用其它正极活性材料、粘结剂和导电剂。因此，本申请并不局限于上面解释和描述的具体实施方式，对本申请的一些修改和变更也应落入本申请的权利要求保护范围。
整个说明书中对“一些实施例”、“部分实施例”、“一个实施例”、“另一举例”、“举例”、“具体举例”或“部分举例”的引用，其所代表的意思是在本申请中的至少一个实施例或举例包含了该实施例或举例中所描述的特定特征、结构、材料或特性。因 此，在整个说明书中的各处所出现的描述，例如：“在一些实施例中”、“在实施例中”、“在一个实施例中”、“在另一个举例中”，“在一个举例中”、“在特定举例中”或“举例“，其不必然是引用本申请中的相同的实施例或示例。此外，本文中的特定特征、结构、材料或特性可以以任何合适的方式在一个或多个实施例或举例中结合。
尽管已经演示和描述了说明性实施例，本领域技术人员应该理解上述实施例不能被解释为对本申请的限制，并且可以在不脱离本申请的精神、原理及范围的情况下对实施例进行改变，替代和修改。

Claims (15)

  1. 一种正极补锂材料，其包括Li 2M1O 2、Li 2M2O 3、Li 5Fe xM3 1-xO 4或Li 6Mn yM4 1-yO 4中的至少一种，
    其中M1包含Ni、Mn、Cu、Fe、Cr或Mo中的至少一种；
    其中M2包含Ni、Mn、Fe、Mo、Zr、Si、Cu、Cr或Ru中的至少一种；
    其中M3包含Al、Nb、Co、Mn、Ni、Mo、Ru或Cr中的至少一种；
    其中M4包含Ni、Fe、Cu或Ru中的至少一种；
    其中0≤x≤1，0≤y≤1。
  2. 根据权利要求1所述的正极补锂材料，其中所述正极补锂材料的首次脱锂容量大于等于300mAh/g。
  3. 根据权利要求1所述的正极补锂材料，其中所述正极补锂材料的中值粒径D50小于等于1.5μm。
  4. 根据权利要求1所述的正极补锂材料，其中所述正极补锂材料包括Li 2NiO 2、Li 2MoO 3、Li 5FeO 4、Li 5Fe 0.9Al 0.1O 4、Li 6MnO 4或Li 6Mn 0.5Ru 0.5O 4中的至少一种。
  5. 一种正极，其包括正极补锂材料层，所述正极补锂材料层包含如权利要求1-4中任意一项所述的正极补锂材料。
  6. 根据权利要求5所述的正极，所述正极补锂材料层的厚度小于等于10μm。
  7. 根据权利要求5所述的正极，其中所述正极补锂材料层还包含导电剂和粘结剂，
    其中所述粘结剂包括聚丙烯、聚乙烯、聚偏氟乙烯、偏氟乙烯-六氟丙烯、聚四氟乙烯或聚六氟丙烯中的至少一种，
    其中所述导电剂包括导电碳黑、碳纤维、乙炔黑、科琴黑、石墨烯或碳纳米管中的至少一种。
  8. 根据权利要求7所述的正极，其中以所述正极补锂材料层的总重量计，所述正极补 锂材料的重量百分比为80wt％-90wt％，所述粘结剂的重量百分比为5wt％-10wt％，所述导电剂的重量百分比为5wt％-10wt％。
  9. 根据权利要求5所述的正极，所述正极还包括正极活性材料层，其中所述正极补锂材料层布置在集流体上，所述正极活性材料层布置在所述正极补锂材料层上。
  10. 根据权利要求9所述的正极，其中所述正极活性材料层包含正极活性材料、粘结剂和导电剂，
    其中所述正极活性材料包括钴酸锂、磷酸铁锂、磷酸锰铁锂、磷酸钒锂、磷酸钒氧锂、钒酸锂、锰酸锂、镍酸锂、镍钴锰酸锂、富锂锰基材料或镍钴铝酸锂中的至少一种，
    其中所述粘结剂包括含氟树脂、聚丙烯树脂、纤维型粘结剂、橡胶型粘结剂或聚酰亚胺型粘结剂中的至少一种，
    其中所述导电剂包括导电碳黑，碳纤维，乙炔黑，科琴黑，石墨烯或碳纳米管中的至少一种。
  11. 根据权利要求10所述的正极，其中以所述正极活性材料层的总重量计，所述正极活性材料的重量百分比为80wt-98wt％，所述粘结剂的重量百分比为0.5wt％-10wt％，所述导电剂的重量百分比为0.5wt％-10wt％。
  12. 根据权利要求10所述的正极，其中所述正极补锂材料层中的所述正极补锂材料占所述正极活性材料层中的所述正极活性材料的1wt％-10wt％。
  13. 一种正极的制备方法，其包括：
    将权利要求1-4中任意一项所述的正极补锂材料沉积或涂布在集流体上；及
    将沉积或涂布有所述正极补锂材料的集流体干燥，然后涂布正极活性材料。
  14. 一种电化学装置，其包括权利要求5-12中任意一项所述的正极或由权利要求13的方法制备得到的正极。
  15. 一种电子装置，其包括权利要求14中所述的电化学装置。
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