WO2018107546A1 - 锂离子电池复合活性物质及其制备方法、锂离子电池电极浆料、正极或负极以及锂离子电池 - Google Patents

锂离子电池复合活性物质及其制备方法、锂离子电池电极浆料、正极或负极以及锂离子电池 Download PDF

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WO2018107546A1
WO2018107546A1 PCT/CN2016/113807 CN2016113807W WO2018107546A1 WO 2018107546 A1 WO2018107546 A1 WO 2018107546A1 CN 2016113807 W CN2016113807 W CN 2016113807W WO 2018107546 A1 WO2018107546 A1 WO 2018107546A1
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ion battery
lithium ion
active material
metal element
group
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PCT/CN2016/113807
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English (en)
French (fr)
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先雪峰
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先雪峰
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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
    • H01M4/362—Composites
    • 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
    • H01M4/133—Electrodes based on carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • 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
    • H01M4/134—Electrodes based on metals, Si or alloys
    • 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
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Definitions

  • the present invention relates to the field of lithium ion battery technology, and in particular to a lithium ion battery composite active material and a preparation method thereof, a lithium ion battery electrode slurry, a positive electrode or a negative electrode, and a lithium ion battery.
  • Lithium-ion battery is a new generation of green high-energy battery, with many advantages such as high voltage, high energy density, long life, small self-discharge, no memory effect, wide operating temperature range, etc., in the field of small mobile energy (such as mobile phones, digital cameras, etc. ), large mobile energy fields (such as plug-in hybrid vehicles, pure electric vehicles, etc.) and fixed energy fields (such as energy storage power stations, UPS, etc.) have broad application prospects.
  • small mobile energy such as mobile phones, digital cameras, etc.
  • large mobile energy fields such as plug-in hybrid vehicles, pure electric vehicles, etc.
  • fixed energy fields such as energy storage power stations, UPS, etc.
  • the high voltage of the lithium ion battery also means that in the state of charge, the positive and negative electrodes of the battery have a large potential difference, which means that the negative electrode is more reductive, the positive electrode is more oxidized, and the thermal stability is worse.
  • high-voltage positive electrode materials such as lithium cobaltate, lithium nickel cobalt aluminum oxide, lithium nickel cobalt manganese oxide, etc., in the case of overcharging, acupuncture, extrusion, etc., it is often caused by heat runaway and even fire. Explosion, there are serious security risks.
  • the object of the present invention is to overcome the defects of low safety and serious safety hazards of the lithium ion battery in the prior art, and provide a lithium ion battery composite active material and a preparation method thereof, a lithium ion battery electrode slurry, and a A positive or negative electrode and a lithium ion battery.
  • the present invention provides a lithium ion battery composite active material, wherein the lithium ion battery composite active material is an additive-coated active material, and the additive is M(OH) a , wherein M is a Group IIA metal element, a Group IB metal element, a Group IIB metal element, a Group IIIB metal element, a Group IVB metal element, a VB group metal element, a Group VIB metal element, a Group VIIB metal element, a Group VIII metal element, a Group IIIA metal At least one of an element, a Group IVA metal element, a Group VA metal element, boron, and silicon, a>0.
  • the present invention provides a method for preparing a lithium ion battery composite active material, which comprises: preparing a hydroxide precipitate of element M, and precipitating the hydroxide of the element M in the presence of a dispersant The active materials are mixed and the resulting mixture is then heat treated.
  • the present invention provides a lithium ion battery electrode slurry, the electrode paste comprising a lithium ion battery active material, a binder, a conductive agent, a solvent, and an optional thickener, wherein the lithium
  • the ion battery active material is a lithium ion battery composite active material according to the present invention.
  • the present invention provides a positive electrode or a negative electrode of a lithium ion battery, the positive electrode or the negative electrode of the lithium ion battery comprising a current collector and an electrode dressing on the current collector, the electrode dressing containing a lithium ion battery active material and bonding The agent, the conductive agent and the optional thickener, wherein the lithium ion battery active material is a lithium ion battery composite active material according to the invention.
  • the present invention provides a lithium ion battery including a battery case and a cell assembly and an electrolyte located inside the battery case, the cell assembly including a positive electrode, a negative electrode, and a diaphragm, and
  • the positive electrode is the positive electrode of the lithium ion battery according to the present invention
  • the negative electrode is the negative electrode of the lithium ion battery according to the present invention.
  • the inventors of the present invention have found in the research that the lithium ion battery composite active material of the present invention (the surface of the active material is coated with the additive of the present invention to prepare a lithium ion battery composite active material) is used as a positive and negative electrode activity.
  • the preparation of the positive electrode and/or the negative electrode of the lithium ion battery can significantly improve the safety of the lithium ion battery thus prepared, and has almost no adverse effect on the conductivity and cycle performance of the lithium ion battery.
  • the present invention provides a lithium ion battery composite active material, wherein the lithium ion battery composite active material is an additive coated active material, and the additive is M(OH) a , wherein M is a Group IIA metal Element, Group IB metal element, Group IIB metal element, Group IIIB metal element, Group IVB metal element, Group VB metal element, Group VIB metal element, Group VIIB metal element, Group VIII metal element, Group IIIA metal element, Group IVA metal At least one of an element, a VA group metal element, boron, and silicon, a>0.
  • M is a Group IIA metal Element, Group IB metal element, Group IIB metal element, Group IIIB metal element, Group IVB metal element, Group VB metal element, Group VIB metal element, Group VIIB metal element, Group VIII metal element, Group IIIA metal element, Group IVA metal At least one of an element, a VA group metal element, boron, and silicon, a>0.
  • the Group IIA metal element is Be and/or Mg
  • the Group IB metal element is Cu
  • the Group IIB metal element is Zn.
  • the Group IIIB metal element is at least one of Y, Sc, La, Ce, Nd, Sm, Gd, and Er
  • the Group IVB metal element is Ti and/or Zr
  • the Group VB metal element is V and / Or Nb
  • the Group VIB metal element is Cr and/or Mo
  • the Group VIIB metal element is Mn
  • the Group VIII metal element is at least one of Fe, Co and Ni
  • the Group IIIA metal element is Al
  • the Group IVA metal element is Sn
  • the VA group metal element is Bi and/or Sb.
  • the inventors of the present invention have found that a lithium ion battery active material having a better safety can be obtained by coating a specific additive on the surface of a lithium ion battery active material, and therefore, in order to further improve the preparation
  • the safety of the obtained lithium ion battery is preferably at least one of aluminum hydroxide, ortho silicic acid and titanium hydroxide.
  • the content of the additive is preferably 0.05-30 by weight based on the weight of the lithium ion battery composite active material.
  • % is further preferably 2-15.3 wt%, and still more preferably 5.7-9.9 wt%.
  • the active material is not particularly limited, and various active materials conventionally used in the art may be used.
  • the active material is a positive electrode active material or a negative electrode active material, and the positive electrode active material
  • the substance is lithium cobaltate, lithium nickel oxide, lithium nickel cobalt oxide, lithium nickel cobalt aluminum oxide, lithium nickel cobalt manganese oxide, lithium nickel manganese oxide, lithium manganate, lithium vanadate, lithium iron phosphate, lithium manganese phosphate, manganese phosphate At least one of iron lithium, lithium iron manganese phosphate, lithium manganese iron cobalt cobalt, lithium manganese iron nickel cobalt, lithium vanadium phosphate, and lithium iron silicate, the negative active material being graphite, lithium titanate, silicon, At least one of hard carbon, tin, and tin oxide.
  • the present invention provides a method for preparing a lithium ion battery composite active material, which comprises: preparing a hydroxide precipitate of an element M, and precipitating the hydroxide of the element M in the presence of a dispersant The active materials are mixed and the resulting mixture is then heat treated.
  • the selection of the element M is the same as the element M in the above-mentioned additive, and the above-mentioned corresponding contents can be referred to, and the detailed description thereof will not be repeated here.
  • the preparation method of the hydroxide precipitate of the different element M is not particularly limited, and various methods commonly used in the art can be used, which are well known to those skilled in the art, and will not be described herein. .
  • the impurities remaining in the hydroxide precipitate of the prepared element M are removed before the hydroxide precipitate of the element M is mixed with the active material.
  • the method of removing impurities therein is not particularly limited and may be various methods commonly used in the art, for example, washing with deionized water to remove impurities therein.
  • the kind of the dispersant is not particularly limited, and may be a solvent used in the process of preparing the hydroxide precipitation of the element M.
  • the dispersant is isopropanol, deionized water, ethanol. At least one of butanol and acetone is further preferably isopropanol or deionized water.
  • the manner in which the hydroxide precipitate of the element M is mixed with the active material is vigorous stirring, and the stirring condition preferably includes a rotation speed of 100 to 400 rpm and a time of 1 to 10 hours.
  • the manner of the heat treatment is not particularly limited, and may be various methods commonly used in the art.
  • the heat treatment is spray drying, microwave drying, fluidized bed drying or oven drying, in order to improve The efficiency is further preferably spray drying.
  • the conditions of the heat treatment may include a temperature of 65 to 200 ° C and a time of 1 s to 12 h.
  • the conditions for spray drying include a temperature of 65-200 ° C and a time of 1-100 s, preferably 1-10 s. For a specific temperature and time, it can be selected according to different heat treatment methods, which are well known to those skilled in the art and will not be described herein.
  • an active material having a surface coated with the foregoing additive can be prepared, that is, a lithium ion battery composite active material can be obtained, and a specific additive can be prepared by controlling the hydroxide precipitation of the element M and the amount of the active material.
  • the content of the lithium ion battery composite active material preferably, the hydroxide precipitation of the control element M and the amount of the active material, so that the content of the additive is 0.05-30% by weight based on the weight of the lithium ion battery composite active material, It is more preferably 2-15.3 wt%, still more preferably 5.7-9.9 wt%.
  • the present invention provides a lithium ion battery electrode slurry, the electrode paste comprising a lithium ion battery active material, a binder, a conductive agent, a solvent, and an optional thickener, wherein the lithium
  • the ion battery active material is a lithium ion battery composite active material according to the present invention.
  • the lithium ion battery electrode slurry of the present invention may be a lithium ion battery positive electrode slurry or a lithium ion battery negative electrode slurry.
  • the selection and amount of the active material, the binder, the conductive agent, the solvent and the thickener are not particularly limited, and may be respectively the corresponding components in the field.
  • the conventional type selection and dosage, for the purpose of considering the energy density of the battery and the comprehensive performance of the battery preferably, the content of the binder on a dry basis is 0.5 based on the weight of the composite active material of the lithium ion battery.
  • the content of the conductive agent is 0.5 to 5% by weight
  • the content of the solvent is 55 to 200% by weight
  • the content of the thickener is 0 to 2.5% by weight.
  • the thickener is generally not used in the lithium-ion battery positive electrode slurry, but is used in the lithium ion battery negative electrode slurry, and the content is 0.5-2.5% by weight based on the weight of the lithium ion battery composite active material.
  • the positive electrode active material in the lithium ion battery composite active material is not particularly limited, and may be various positive electrode active materials as described above, and the description thereof will not be repeated here.
  • the negative electrode active material in the lithium ion battery composite active material is not particularly limited, and may be various negative electrode active materials as described above, and the description thereof will not be repeated here.
  • the binder is not particularly limited, and various binders conventionally used in the art may be used.
  • the binder is polyacrylamide or poly.
  • At least one of vinylidene fluoride, polytetrafluoroethylene, styrene butadiene rubber, cellulose-based polymer, polyvinyl alcohol, polyolefin, fluorinated rubber, and polyurethane the cellulose-based polymer may be selected from methyl cellulose One or more of ethyl cellulose, hydroxypropyl methyl cellulose, and hydroxypropyl ethyl cellulose.
  • the binder is a polymer, the number average molecular weight of each polymer is generally It is 30-1.5 million.
  • the conductive agent is not particularly limited, and various conductive agents conventionally used in the art may be used.
  • the conductive agent is Ketjen black, acetylene black, and graphite. At least one of an olefin, a carbon nanotube, a carbon fiber (VGCF), microcrystalline graphite, and conductive carbon black (Super-P).
  • the solvent is not particularly limited and may be various solvents conventionally used in the art.
  • the solvent is N-methylpyrrolidone (NMP), deionized water, tetrahydrofuran, dimethyl sulfoxide, ethanol, and the like. At least one of propanol.
  • NMP N-methylpyrrolidone
  • the solvent is N-methylpyrrolidone; and in the lithium ion battery negative electrode slurry, the solvent is deionized water and/or N-methylpyrrolidone.
  • the thickener is mostly used in the negative electrode slurry of the lithium ion battery, and whether or not the thickener is added to the positive electrode slurry of the lithium ion battery can be selected according to the actual application, and the specific selection is well known to those skilled in the art, and preferably,
  • the thickener is at least one of sodium carboxymethyl cellulose (CMC), polyvinylpyrrolidone, polyethylene glycol, and polyvinyl alcohol.
  • the method for preparing the lithium ion battery electrode slurry of the present invention is not particularly limited, and various methods commonly used in the art may be used as long as the slurry containing the above components can be uniformly mixed, for example, containing lithium ions.
  • a slurry of a battery composite active material, a binder, a conductive agent, a solvent, and an optional thickener may be obtained by first mixing a binder and a solvent to obtain a mixed liquid, and then combining the active material of the lithium ion battery with the conductive agent and
  • the optional thickener is mixed with the mixed solution, or may be mixed by adding a thickener or a binder and a solvent to obtain a mixed liquid, and then the lithium ion battery composite active material, the conductive agent, and the binder or thickener Mix with the mixture.
  • the present invention provides a positive electrode or a negative electrode of a lithium ion battery, the positive electrode or the negative electrode of the lithium ion battery comprising a current collector and an electrode dressing on the current collector, the electrode dressing containing a lithium ion battery active material and bonding The agent, the conductive agent and the optional thickener, wherein the lithium ion battery active material is a lithium ion battery composite active material according to the invention.
  • the content of the additive is 0.05-25 by weight based on the dry weight of the electrode dressing. % is further preferably 2 to 14% by weight, more preferably 5 to 9% by weight. It will be understood by those skilled in the art that the dry weight of the electrode dressing refers to the weight of the material obtained after drying all of the slurry coated on the current collector.
  • the method for preparing the positive electrode or the negative electrode of the lithium ion battery is not particularly limited, and may be various methods commonly used in the art, for example, may include: coating the lithium ion battery electrode slurry of the present invention on a current collector, drying.
  • the current collector is not particularly limited, and various positive electrode current collectors commonly used in the art may be used.
  • the positive electrode current collector may be aluminum foil.
  • the current collector is not particularly limited, and various negative electrode current collectors commonly used in the art may be used.
  • the negative electrode current collector may be a copper foil.
  • the method for drying is not particularly limited and may be various methods commonly used in the art.
  • the drying conditions include: a temperature of 80-180 ° C.
  • the present invention provides a lithium ion battery including a battery case and a cell assembly and an electrolyte located inside the battery case, the cell assembly including a positive electrode, a negative electrode, and a diaphragm, and
  • the positive electrode is the positive electrode of the lithium ion battery according to the present invention
  • the negative electrode is the negative electrode of the lithium ion battery according to the present invention.
  • the positive electrode and the negative electrode is a positive electrode or a negative electrode prepared by the lithium ion battery composite active material of the present invention, that is, the positive electrode is The positive electrode of the lithium ion battery according to the invention, or the negative electrode is the negative electrode of the lithium ion battery according to the invention, or the positive electrode and the negative electrode are respectively the positive electrode and the negative electrode of the lithium ion battery according to the invention.
  • the separator and the electrolytic solution forming the lithium ion battery may be a separator and a nonaqueous electrolyte which are conventionally used in the art.
  • the separator is disposed between the positive electrode and the negative electrode, and has electrical insulating properties and liquid retaining properties, and the cell assembly and the non-aqueous electrolyte are housed together in the battery can.
  • the separator may be various separators commonly used in the art, such as a polymer microporous film, including a polypropylene microporous film and a multilayer composite microporous film of polypropylene and polyethylene. The position, nature and type of the separator are well known to those skilled in the art and will not be described herein.
  • the nonaqueous electrolytic solution is a mixed solution of an electrolyte lithium salt and a nonaqueous solvent, and it is not particularly limited, and a conventional nonaqueous electrolytic solution in the art can be used.
  • the electrolyte lithium salt is selected from one or more of lithium hexafluorophosphate (LiPF 6 ), lithium perchlorate, lithium tetrafluoroborate, lithium hexafluoroarsenate, lithium halide, lithium chloroaluminate, and lithium fluorocarbon sulfonate.
  • the non-aqueous solvent is a mixed solution of a chain acid ester and a cyclic acid ester, wherein the chain acid ester may be dimethyl carbonate (DMC), diethyl carbonate (DEC), ethyl methyl carbonate (EMC), and methyl propylene carbonate.
  • DMC dimethyl carbonate
  • DEC diethyl carbonate
  • EMC ethyl methyl carbonate
  • methyl propylene carbonate At least one of ester (MPC), dipropyl carbonate (DPC) and other fluorine-containing, sulfur-containing or unsaturated chain-containing chain organic esters
  • the cyclic acid ester may be ethylene carbonate (EC) or carbonic acid.
  • the injection amount of the electrolyte is generally 5-8 g/amperes, and the concentration of the electrolyte is generally 0.8-1.2 mol/liter.
  • the battery case is not particularly limited, and various battery cases commonly used in the art can be used, which are well known to those skilled in the art and will not be described herein.
  • the method for preparing the battery is a common method in the art.
  • the positive electrode and the negative electrode and the separator form a cell assembly, and the obtained cell assembly and non-aqueous electrolyte are sealed in the battery case.
  • the specific methods are well known to those skilled in the art and will not be described herein.
  • Lithium nickel cobalt manganese oxide LiNi 0.5 Co 0.2 Mn 0.3 O 2 was purchased from Shanghai Shanshan Technology Co., Ltd.
  • Lithium cobaltate LiCoO 2 was purchased from Tianjin Bamo Technology Co., Ltd.
  • Lithium nickel cobalt aluminum oxide LiNi 0.8 Co 0.15 Al 0.05 O 2 was purchased from Toda Industry Co., Ltd., Japan.
  • the Pvdf binder HSV900 was purchased from Arkema, France.
  • the PTFE emulsion binder D210 had a solid content of 60% and was purchased from Daikin Industries Co., Ltd., Japan.
  • the conductive agent Super-P was purchased from the Swiss company Temco.
  • Natural graphite was purchased from Shenzhen Beitray New Energy Materials Co., Ltd.
  • the thickener CMC was purchased from Japan Daiichi Pharmaceutical Co., Ltd.
  • the styrene-butadiene rubber latex binder has a solid content of 50% and was purchased from Japan Rayon Co., Ltd.
  • the positive electrode slurry was uniformly coated on an aluminum foil having a thickness of 25 ⁇ m, the coating width was 160 mm, and the double-sided surface density of the dressing was 331.4 g/m 2 (the double-sided surface density of the dressing was measured by the weight after drying, the same below, The content of the additive was about 7.5 wt% based on the dry weight of the electrode dressing, and then dried at 110 ° C to obtain a positive electrode tab.
  • the specific method is: first dissolve the thickener CMC with 12500g deionized water as solvent And stirring, respectively, the styrene-butadiene rubber latex binder, the conductive agent Super-P, the natural graphite anode material and the above thickener solution are mixed, and then stirred to form a uniform anode slurry;
  • the negative electrode slurry was uniformly coated on a copper foil having a thickness of 18 ⁇ m, the coating width was 164 mm, and the double-sided surface density of the dressing was 165 g/m 2 (based on the weight after drying, the same below), and then at 100 ° C. Drying is carried out to obtain a negative electrode tab.
  • the positive electrode piece is cut into a size of 120 mm ⁇ 160 mm as a positive electrode
  • the negative electrode piece is cut into a size of 125 mm ⁇ 164 mm as a negative electrode
  • a polypropylene film is used as a separator, assembled into a battery core assembly, and placed in a soft aluminum-plastic film battery case.
  • the positive and negative poles are respectively welded with the aluminum plastic film, and the insulation between the polar ear and the battery case is ensured in the process.
  • the weight of the active component lithium nickel cobalt manganese oxide in the positive electrode material is about 191 g.
  • the weight of the negative electrode active material natural graphite was about 104 g, and the nominal capacity of the battery was 30 Ah.
  • the battery was aged at 45 ° C for 48 hours, then charged to 4.00 V with a current of 0.6 A, and then aged for another 48 hours at 45 ° C. Finally, the battery was produced under the protection of a nitrogen atmosphere. The gas was taken out and the battery was sealed twice to obtain a lithium ion battery A1.
  • a lithium ion battery A2 was prepared according to the method of Example 1, except that the positive electrode composite active material of LiNi 0.80 Co 0.15 Al 0.05 O 2 was coated with ortho silicic acid (Si(OH) 4 ) instead of aluminum hydroxide coated LiNi 0.5.
  • a positive electrode composite active material of Co 0.2 Mn 0.3 O 2 wherein a positive electrode composite active material of ortho silicic acid (Si(OH) 4 ) coated with LiNi 0.80 Co 0.15 Al 0.05 O 2 is prepared as follows:
  • a lithium ion battery A3 was prepared according to the method of Example 1, except that the positive electrode composite active material coated with lithium hydroxide (Ti(OH) 4 ) was replaced by aluminum hydroxide to coat LiNi 0.5 Co 0.2 Mn 0.3 O.
  • a positive electrode composite active material of 2 wherein a positive electrode composite active material of titanium oxyhydroxide (Ti(OH) 4 ) coated with lithium cobaltate is prepared as follows:
  • the mixture was vigorously stirred at 360 rpm for 2 hours, and spray-dried to obtain a positive electrode composite active material of titanium hydroxide (Ti(OH) 4 ) coated with lithium cobaltate (the content of the additive was 7.8% by weight based on the weight of the composite active material) .
  • a lithium ion battery A4 was prepared according to the method of Example 1, except that (1) LiNi 0.5 Co 0.2 Mn 0.3 O 2 lithium nickel cobalt manganese oxide cathode material was not surface coated with an additive, and the battery positive electrode sheet preparation was not carried out. Surface coated LiNi 0.5 Co 0.2 Mn 0.3 O 2 lithium nickel cobalt manganese oxide cathode material, and the double-sided surface density of the dressing is 305.5 g/m 2 when the battery positive electrode sheet is prepared; (2) preparation of the battery negative electrode sheet Methods as below:
  • the precipitate was washed with deionized water to remove ammonium nitrate therein, water was replaced with isopropyl alcohol, and 9220 g of a natural graphite negative electrode material as an active ingredient was added to the precipitate, and 12,000 g of isopropyl alcohol was added thereto, and vigorous stirring was continued at 330 rpm for 2 hours.
  • Spray drying was carried out to obtain a negative electrode composite active material of aluminum hydroxide (Al(OH) 3 ) coated with natural graphite (the content of the additive was 7.8% by weight based on the weight of the composite active material).
  • the specific method is: first The thickener CMC was dissolved in 12500 g of deionized water as a solvent, and the styrene-butadiene rubber latex binder, the conductive agent Super-P, the negative electrode composite active material and the thickener solution were separately mixed under stirring, followed by stirring. Forming a uniform negative electrode slurry;
  • the negative electrode slurry was uniformly coated on a copper foil having a thickness of 18 ⁇ m, a coating width of 164 mm, a double-sided surface density of the dressing of 179 g/m 2 , and then dried at 100 ° C to obtain a negative electrode tab.
  • a lithium ion battery A5 was prepared in the same manner as in Example 1, except that (1) a positive electrode composite active material coated with an aluminum hydroxide additive was prepared as follows:
  • a lithium ion battery A6 was prepared in the same manner as in Example 1, except that (1) a positive electrode composite active material coated with an aluminum hydroxide additive was prepared as follows:
  • a lithium ion battery A7 was prepared in the same manner as in Example 1, except that (1) a positive electrode composite active material coated with an aluminum hydroxide additive was prepared as follows:
  • 3750g of aluminum nitrate nonahydrate was dissolved in 10000g of deionized water to prepare aluminum nitrate solution. Under stirring condition, ammonia solution with a mass fraction of 25% was gradually added to the aluminum nitrate solution until the pH value of the reaction system was 7.3, and ammonia was controlled. The time was 2 hours, and after completion of the reaction, precipitation of aluminum hydroxide was obtained. The precipitate was washed with deionized water to remove ammonium nitrate therein, and water was replaced with isopropyl alcohol, and 38220 g of a lithium nickel cobalt manganese oxide positive electrode material having a chemical formula of LiNi 0.5 Co 0.2 Mn 0.3 O 2 as an active component was added to the precipitate.
  • a lithium ion battery A8 was prepared in the same manner as in Example 1, except that (1) a positive electrode composite active material coated with an aluminum hydroxide additive was prepared as follows:
  • a lithium ion battery A9 was prepared in the same manner as in Example 1, except that (1) a positive electrode composite active material coated with an aluminum hydroxide additive was prepared as follows:
  • a lithium ion battery A10 was prepared according to the method of Example 1, except that the positive electrode composite active material of LiNi 0.5 Co 0.2 Mn 0.3 O 2 was coated with ytterbium hydroxide (Y(OH) 3 ) instead of aluminum hydroxide coated LiNi 0.5.
  • a positive electrode composite active material of Co 0.2 Mn 0.3 O 2 wherein a positive electrode composite active material of lanthanum hydroxide (Y(OH) 3 ) coated with LiNi 0.5 Co 0.2 Mn 0.3 O 2 is prepared as follows:
  • the precipitate was washed with deionized water to remove ammonium nitrate therein, and 16537 g of a lithium nickel cobalt manganese oxide positive electrode material having a chemical formula of LiNi 0.5 Co 0.2 Mn 0.3 O 2 as an active ingredient was added to the precipitate, and 19,000 g of water was added thereto, and the strength was continued at 360 rpm.
  • the cathode active material of the dried yttrium hydroxide (Y(OH) 3 ) coated with LiNi 0.5 Co 0.2 Mn 0.3 O 2 was obtained by spray drying (based on the weight of the composite active material, the content of the additive was 7.8 wt%).
  • a lithium ion battery A11 was prepared according to the method of Example 1, except that a positive electrode composite active material coated with LiNi 0.5 Co 0.2 Mn 0.3 O 2 with strontium hydroxide (Sc(OH) 3 ) was used instead of aluminum hydroxide coated LiNi 0.5.
  • a positive electrode composite active material of Co 0.2 Mn 0.3 O 2 in which a positive electrode composite active material of lanthanum hydroxide (Sc(OH) 3 ) coated with LiNi 0.5 Co 0.2 Mn 0.3 O 2 is prepared as follows:
  • the precipitate was washed with deionized water to remove ammonium nitrate therein, and 11348 g of a lithium nickel cobalt manganese oxide positive electrode material having a chemical formula of LiNi 0.5 Co 0.2 Mn 0.3 O 2 as an active ingredient was added to the precipitate, and 14,000 g of water was added thereto, and the strength was continued at 290 rpm.
  • the cathode active material of the dried lanthanum hydroxide (Sc(OH) 3 ) coated with LiNi 0.5 Co 0.2 Mn 0.3 O 2 was obtained by spray drying (based on the weight of the composite active material, the content of the additive was 7.8 wt%).
  • a lithium ion battery A12 was prepared according to the method of Example 1, except that the positive electrode composite active material of LiNi 0.5 Co 0.2 Mn 0.3 O 2 was coated with zirconium hydroxide (Zr(OH) 4 ) instead of aluminum hydroxide coated LiNi 0.5.
  • a positive electrode composite active material of Co 0.2 Mn 0.3 O 2 in which a positive electrode composite active material of zirconium hydroxide (Zr(OH) 4 ) coated with LiNi 0.5 Co 0.2 Mn 0.3 O 2 is prepared as follows:
  • the precipitate was washed with deionized water to remove sodium chloride, and isopropyl alcohol was added to replace the water, and 18795 g of a lithium nickel cobalt manganese oxide positive electrode material having a chemical formula of LiNi 0.5 Co 0.2 Mn 0.3 O 2 as an active ingredient was added to the precipitate. 21,000g of isopropanol was added, and the mixture was vigorously stirred at 350 rpm for 2 hours. Finally, the cathode composite active material of dry zirconium hydroxide (Zr(OH) 4 ) coated with LiNi 0.5 Co 0.2 Mn 0.3 O 2 was obtained by spray drying (to composite The content of the additive was 7.8% by weight based on the weight of the active material.
  • Zr(OH) 4 dry zirconium hydroxide
  • the oxygen positive electrode material was added thereto, and 14,000 g of isopropyl alcohol was added thereto, and the mixture was vigorously stirred at 270 rpm for 2 hours. Finally, the dry cathode of the vanadium hydroxide (V(OH) 3 ) coated with LiNi 0.5 Co 0.2 Mn 0.3 O 2 was obtained by spray drying.
  • the active material (the content of the additive was 7.8% by weight based on the weight of the composite active material).
  • a lithium ion battery A14 was prepared according to the method of Example 1, except that a positive electrode composite active material of LiNi 0.5 Co 0.2 Mn 0.3 O 2 was coated with lanthanum hydroxide (La(OH) 3 ) instead of aluminum hydroxide coated LiNi 0.5.
  • a positive electrode composite active material of Co 0.2 Mn 0.3 O 2 in which a positive electrode composite active material of lanthanum hydroxide (La(OH) 3 ) coated with LiNi 0.5 Co 0.2 Mn 0.3 O 2 is prepared as follows:
  • cerium nitrate hexahydrate 4330 g was dissolved in 20,000 g of deionized water to prepare a cerium nitrate solution. Under stirring, a mass fraction of 25% ammonia water was gradually added to the cerium nitrate solution until the pH of the reaction system was 7.3, and ammonia was controlled. The time was 2 hours, and after completion of the reaction, precipitation of cesium hydroxide was obtained.
  • the precipitate was washed with deionized water to remove ammonium nitrate therein, and 22447 g of a lithium nickel cobalt manganese oxide positive electrode material having a chemical formula of LiNi 0.5 Co 0.2 Mn 0.3 O 2 as an active ingredient was added thereto, and 25000 g of deionized water was added thereto, and the mixture was further heated at 300 rpm. Stirring vigorously for 2 hours, and finally by spray drying to obtain a dry composite active material of dried lanthanum hydroxide (La(OH) 3 ) coated with LiNi 0.5 Co 0.2 Mn 0.3 O 2 (based on the weight of the composite active material, the content of the additive) It is 7.8% by weight).
  • La(OH) 3 dried lanthanum hydroxide
  • a lithium ion battery A15 was prepared according to the method of Example 1, except that the positive electrode composite active material of LiNi 0.5 Co 0.2 Mn 0.3 O 2 was coated with cesium hydroxide (Ce(OH) 3 ) instead of aluminum hydroxide coated LiNi 0.5.
  • a positive electrode composite active material of Co 0.2 Mn 0.3 O 2 in which a positive electrode composite active material of lanthanum hydroxide (Ce(OH) 3 ) coated with LiNi 0.5 Co 0.2 Mn 0.3 O 2 is prepared as follows:
  • cerium nitrate hexahydrate 4340g was dissolved in 15000g of deionized water to prepare a cerium nitrate solution. Under stirring, the ammonia solution with a mass fraction of 25% was gradually added to the cerium nitrate solution until the pH of the reaction system was 7.3, and the ammonia was controlled. The time was 2 hours, and after completion of the reaction, precipitation of cesium hydroxide was obtained.
  • the precipitate was washed with deionized water to remove ammonium nitrate therein, and 22589 g of a lithium nickel cobalt manganese oxide positive electrode material having a chemical formula of LiNi 0.5 Co 0.2 Mn 0.3 O 2 as an active ingredient was added thereto, and 25000 g of deionized water was added thereto, and 330 rpm was continued. Stirring vigorously for 2 hours, finally by spray drying to obtain dried cerium hydroxide (Ce(OH) 3 ) coated LiNi 0.5 Co 0.2 Mn 0.3 O 2 positive electrode composite active material (based on the weight of the composite active material, the content of the additive) It is 7.8% by weight).
  • Ce(OH) 3 cerium hydroxide
  • a lithium ion battery A16 was prepared according to the method of Example 1, except that a positive electrode composite active material coated with LiNi 0.5 Co 0.2 Mn 0.3 O 2 with ytterbium hydroxide (Nd(OH) 3 ) was used instead of aluminum hydroxide to coat LiNi 0.5.
  • a positive electrode composite active material of Co 0.2 Mn 0.3 O 2 in which a positive electrode composite active material of lanthanum hydroxide (Nd(OH) 3 ) coated with LiNi 0.5 Co 0.2 Mn 0.3 O 2 is prepared as follows:
  • the precipitate was washed with deionized water to remove ammonium nitrate therein, and 23074 g of a lithium nickel cobalt manganese oxide positive electrode material having a chemical formula of LiNi 0.5 Co 0.2 Mn 0.3 O 2 as an active ingredient was added thereto, and 25000 g of deionized water was added thereto, and 330 rpm was continued. Stirring vigorously for 2 hours, and finally by spray drying to obtain a dry cathode active material of Nd(OH) 3 coated LiNi 0.5 Co 0.2 Mn 0.3 O 2 (based on the weight of the composite active material, the content of the additive) It is 7.8% by weight).
  • a lithium ion battery A17 was prepared according to the method of Example 1, except that the positive electrode composite active material of LiNi 0.5 Co 0.2 Mn 0.3 O 2 was coated with barium hydroxide (Sm(OH) 3 ) instead of aluminum hydroxide coated LiNi 0.5.
  • a positive electrode composite active material of Co 0.2 Mn 0.3 O 2 in which a positive electrode composite active material of lanthanum hydroxide (Sm(OH) 3 ) coated with LiNi 0.5 Co 0.2 Mn 0.3 O 2 is prepared as follows:
  • cerium nitrate hexahydrate 4440g was dissolved in 15000g of deionized water to prepare a cerium nitrate solution. Under stirring, the ammonia solution with a mass fraction of 25% was gradually added to the cerium nitrate solution until the pH of the reaction system was 7.3, and the ammonia was controlled. The time was 2 hours, and after completion of the reaction, precipitation of cesium hydroxide was obtained.
  • the precipitate was washed with deionized water to remove ammonium nitrate therein, and 23807 g of a lithium nickel cobalt manganese oxide positive electrode material having a chemical formula of LiNi 0.5 Co 0.2 Mn 0.3 O 2 as an active ingredient was added thereto, and 26,000 g of deionized water was added thereto, and 340 rpm was continued. Stirring vigorously for 2 hours, and finally by spray drying to obtain a dry cathode active material of Sm(OH) 3 coated with LiNi 0.5 Co 0.2 Mn 0.3 O 2 (based on the weight of the composite active material, the content of the additive) It is 7.8% by weight).
  • a lithium ion battery A18 was prepared according to the method of Example 1, except that a positive electrode composite active material coated with lanthanum hydroxide (Gd(OH) 3 ) and LiNi 0.5 Co 0.2 Mn 0.3 O 2 was used instead of aluminum hydroxide to coat LiNi 0.5.
  • a positive electrode composite active material of Co 0.2 Mn 0.3 O 2 in which a positive electrode composite active material of lanthanum hydroxide (Gd(OH) 3 ) coated with LiNi 0.5 Co 0.2 Mn 0.3 O 2 is prepared as follows:
  • the precipitate was washed with deionized water to remove ammonium nitrate therein, and 24622 g of a lithium nickel cobalt manganese oxide positive electrode material having a chemical formula of LiNi 0.5 Co 0.2 Mn 0.3 O 2 as an active ingredient was added thereto, and 27,000 g of deionized water was added thereto, and 290 rpm was continued. Stirring vigorously for 2 hours, finally by spray drying to obtain dried ytterbium hydroxide (Gd(OH) 3 ) coated LiNi 0.5 Co 0.2 Mn 0.3 O 2 cathode composite active material (based on the weight of the composite active material, the content of the additive It is 7.8% by weight).
  • Gd(OH) 3 dried ytterbium hydroxide
  • a lithium ion battery A19 was prepared according to the method of Example 1, except that the positive electrode composite active material of LiNi 0.5 Co 0.2 Mn 0.3 O 2 was coated with lanthanum hydroxide (Er(OH) 3 ) instead of aluminum hydroxide coated LiNi 0.5.
  • a positive electrode composite active material of Co 0.2 Mn 0.3 O 2 in which a positive electrode composite active material of lanthanum hydroxide (Er(OH) 3 ) coated with LiNi 0.5 Co 0.2 Mn 0.3 O 2 is prepared as follows:
  • cerium nitrate pentahydrate 4443g was dissolved in 15000g of deionized water to prepare a cerium nitrate solution. Under stirring, a mass fraction of 25% ammonia water was gradually added to the cerium nitrate solution until the pH of the reaction system was 7.3. The time was 2 hours, and after completion of the reaction, precipitation of cesium hydroxide was obtained.
  • the precipitate was washed with deionized water to remove ammonium nitrate therein, and 25804 g of a lithium nickel cobalt manganese oxide positive electrode material having a chemical formula of LiNi 0.5 Co 0.2 Mn 0.3 O 2 as an active ingredient was added thereto, and 28000 g of deionized water was added thereto, and 280 rpm was continued. Stirring vigorously for 2 hours, finally by spray drying to obtain dried ytterbium hydroxide (Er(OH) 3 ) coated LiNi 0.5 Co 0.2 Mn 0.3 O 2 cathode composite active material (based on the weight of the composite active material, the content of the additive It is 7.8% by weight).
  • Er(OH) 3 dried ytterbium hydroxide
  • a lithium ion battery A20 was prepared according to the method of Example 1, except that the positive electrode composite active material of LiNi 0.5 Co 0.2 Mn 0.3 O 2 was coated with lanthanum hydroxide (Nb(OH) 5 ) instead of aluminum hydroxide coated LiNi 0.5.
  • a positive electrode composite active material of Co 0.2 Mn 0.3 O 2 in which a positive electrode composite active material of lanthanum hydroxide (Nb(OH) 5 ) coated with LiNi 0.5 Co 0.2 Mn 0.3 O 2 is prepared as follows:
  • the precursor was washed with deionized water to remove ammonium nitrate and ammonium fluoride therein, and then 21034 g of a lithium nickel cobalt manganese oxide positive electrode material having a chemical formula of LiNi 0.5 Co 0.2 Mn 0.3 O 2 as an active component was added thereto, and 24,000 g was added thereto.
  • Deionized water vigorously stirred at 380 rpm for 2 hours, and finally by spray drying to obtain dried ytterbium hydroxide (Nb(OH) 5 ) coated LiNi 0.5 Co 0.2 Mn 0.3 O 2 cathode composite active material (by the weight of the composite active material)
  • the standard, the content of the additive was 7.8% by weight).
  • a lithium ion battery A21 was prepared according to the method of Example 1, except that a positive electrode composite active material coated with chromium hydroxide (Cr(OH) 3 ) of LiNi 0.5 Co 0.2 Mn 0.3 O 2 was used instead of aluminum hydroxide to coat LiNi 0.5.
  • a positive electrode composite active material of Co 0.2 Mn 0.3 O 2 in which a positive electrode composite active material in which chromium hydroxide (Cr(OH) 3 ) is coated with LiNi 0.5 Co 0.2 Mn 0.3 O 2 is prepared as follows:
  • chromium nitrate nonahydrate 4000g was dissolved in 15000g of deionized water to prepare a chromium nitrate solution. Under stirring, the ammonia solution with a mass fraction of 25% was gradually added to the chromium nitrate solution until the pH of the reaction system was 7.3, and the ammonia was controlled. The time was 2 hours, and after completion of the reaction, chromium hydroxide was precipitated.
  • the precipitate was washed with deionized water to remove ammonium nitrate therein, and 12175 g of a lithium nickel cobalt manganese oxide positive electrode material having a chemical formula of LiNi 0.5 Co 0.2 Mn 0.3 O 2 as an active ingredient was added thereto, and 14,000 g of deionized water was added thereto, and the flow was continued at 250 rpm. Stirring vigorously for 2 hours, and finally by spray drying to obtain a dry cathode active material of Cr(OH) 3 coated with LiNi 0.5 Co 0.2 Mn 0.3 O 2 (based on the weight of the composite active material, the content of the additive) It is 7.8% by weight).
  • a lithium ion battery A22 was prepared according to the method of Example 1, except that a positive electrode composite active material coated with molybdenum hydroxide (Mo(OH) 3 ) and LiNi 0.5 Co 0.2 Mn 0.3 O 2 was used instead of aluminum hydroxide to coat LiNi 0.5.
  • a positive electrode composite active material of Co 0.2 Mn 0.3 O 2 wherein a positive electrode composite active material in which molybdenum hydroxide (Mo(OH) 3 ) is coated with LiNi 0.5 Co 0.2 Mn 0.3 O 2 is prepared as follows:
  • a lithium ion battery A23 was prepared according to the method of Example 1, except that the positive electrode composite active material of LiNi 0.5 Co 0.2 Mn 0.3 O 2 was coated with manganese hydroxide (Mn(OH) 2 ) instead of aluminum hydroxide coated LiNi.
  • a positive electrode composite active material of 0.5 Co 0.2 Mn 0.3 O 2 wherein a positive electrode composite active material of manganese oxide (Mn(OH) 2 ) coated with LiNi 0.5 Co 0.2 Mn 0.3 O 2 is prepared as follows:
  • 3580g of a 50% by weight aqueous solution of manganese nitrate was diluted with 15000g of deionized water to prepare a manganese nitrate solution.
  • ammonia water with a mass fraction of 25% was gradually added to the manganese nitrate solution until The pH of the reaction system was 7.3, and the time for adding ammonia was controlled to be 2 hours. After the reaction was completed, manganese hydroxide precipitate was obtained.
  • the precipitate was washed with deionized water under nitrogen to remove ammonium nitrate therein, and water was replaced with isopropyl alcohol, followed by 10,513 g of lithium nickel cobalt manganese oxide having a chemical formula of LiNi 0.5 Co 0.2 Mn 0.3 O 2 as an active ingredient.
  • the positive electrode material was added thereto, 13,000 g of isopropyl alcohol was added, and the mixture was vigorously stirred at 240 rpm for 2 hours.
  • the positive electrode composite activity of dried manganese hydroxide (Mn(OH) 2 ) coated with LiNi 0.5 Co 0.2 Mn 0.3 O 2 was obtained by spray drying.
  • the substance (the content of the additive is 7.8% by weight based on the weight of the composite active material).
  • a lithium ion battery A24 was prepared according to the method of Example 1, except that the positive electrode composite active material of LiNi 0.5 Co 0.2 Mn 0.3 O 2 coated with iron hydroxide (Fe(OH) 3 ) was used instead of the hydroxy aluminum hydroxide coated LiNi.
  • a positive electrode composite active material of 0.5 Co 0.2 Mn 0.3 O 2 wherein a positive electrode composite active material in which iron hydroxide (Fe(OH) 3 ) is coated with LiNi 0.5 Co 0.2 Mn 0.3 O 2 is prepared as follows:
  • ferric nitrate nonahydrate was dissolved in 15000g of deionized water to prepare a ferric nitrate solution. Under the condition of vigorous stirring at 260 rpm, a mass fraction of 25% ammonia water was quickly added to the ferric nitrate solution until the pH of the reaction system was 11. A precipitate was obtained after completion of the reaction. The precipitate was quickly washed with deionized water to remove ammonium nitrate and ammonia water therein, and water was replaced with isopropyl alcohol, and 12630 g of lithium nickel cobalt manganese oxide cathode material having a chemical formula of LiNi 0.5 Co 0.2 Mn 0.3 O 2 was added as an active ingredient.
  • a lithium ion battery A25 was prepared according to the method of Example 1, except that the positive electrode composite active material of LiNi 0.5 Co 0.2 Mn 0.3 O 2 was coated with cobalt oxychloride (Co(OH) 2 ) instead of aluminum hydroxide coated LiNi.
  • a positive electrode composite active material of 0.5 Co 0.2 Mn 0.3 O 2 wherein a positive electrode composite active material in which Cobalt oxyhydroxide (Co(OH) 2 ) is coated with LiNi 0.5 Co 0.2 Mn 0.3 O 2 is prepared as follows:
  • the manganese oxide positive electrode material was added thereto, 13,000 g of isopropanol was added, and the mixture was vigorously stirred at 290 rpm for 2 hours. Finally, the dried cobalt oxide (Co(OH) 2 ) coated with the positive electrode of LiNi 0.5 Co 0.2 Mn 0.3 O 2 was obtained by spray drying.
  • the composite active material (the content of the additive is 7.8% by weight based on the weight of the composite active material).
  • a lithium ion battery A26 was prepared according to the method of Example 1, except that a positive electrode composite active material coated with nickel hydroxide (Ni(OH) 2 ) and LiNi 0.5 Co 0.2 Mn 0.3 O 2 was used instead of aluminum hydroxide to coat LiNi.
  • a positive electrode composite active material of 0.5 Co 0.2 Mn 0.3 O 2 wherein a positive electrode composite active material in which nickel hydroxide (Ni(OH) 2 ) is coated with LiNi 0.5 Co 0.2 Mn 0.3 O 2 is prepared as follows:
  • 2910g of nickel hexahydrate hexahydrate was dissolved in 15000g of deionized water to prepare a nickel nitrate solution. Under stirring and nitrogen protection, ammonia solution with a mass fraction of 25% was gradually added to the nickel nitrate solution until the reaction system The pH value was 7.3, and the time for adding ammonia was controlled to be 2 hours. After the completion of the reaction, nickel hydroxide precipitation was obtained. The precipitate was washed with deionized water under nitrogen atmosphere to remove ammonium nitrate therein, and water was replaced with isopropyl alcohol, followed by 10956 g of lithium nickel cobalt having a chemical formula of LiNi 0.5 Co 0.2 Mn 0.3 O 2 as an active ingredient.
  • the manganese oxide positive electrode material was added thereto, 13,000 g of isopropyl alcohol was added, and the mixture was vigorously stirred at 300 rpm for 2 hours. Finally, the dried nickel hydroxide (Ni(OH) 2 ) coated with the positive electrode of LiNi 0.5 Co 0.2 Mn 0.3 O 2 was obtained by spray drying.
  • the composite active material (the content of the additive is 7.8% by weight based on the weight of the composite active material).
  • a lithium ion battery A27 was prepared according to the method of Example 1, except that a positive electrode composite active material coated with tin hydroxide (Sn(OH) 4 ) and LiNi 0.5 Co 0.2 Mn 0.3 O 2 was used instead of aluminum hydroxide to coat LiNi 0.5.
  • a positive electrode composite active material of Co 0.2 Mn 0.3 O 2 in which a positive electrode composite active material in which tin hydroxide (Sn(OH) 4 ) is coated with LiNi 0.5 Co 0.2 Mn 0.3 O 2 is prepared as follows:
  • a lithium ion battery A28 was prepared according to the method of Example 1, except that the positive electrode composite active material of LiNi 0.5 Co 0.2 Mn 0.3 O 2 was coated with barium hydroxide (Bi(OH) 3 ) instead of aluminum hydroxide coated LiNi 0.5.
  • a positive electrode composite active material of Co 0.2 Mn 0.3 O 2 wherein a positive electrode composite active material of lanthanum hydroxide (Bi(OH) 3 ) coated with LiNi 0.5 Co 0.2 Mn 0.3 O 2 is prepared as follows:
  • lanthanum nitrate pentahydrate 4850g was added to a 2% mass fraction of 20,000 g of dilute nitric acid aqueous solution to prepare a cerium nitrate solution.
  • the cerium nitrate solution was quickly added to 2600 g of 25% by mass ammonia water under vigorous stirring at 330 rpm. After completion, a precipitate of cesium hydroxide was obtained.
  • the precipitate was washed with deionized water to remove ammonium nitrate and ammonia water therein, and then 30733 g of a lithium nickel cobalt manganese oxide positive electrode material having a chemical formula of LiNi 0.5 Co 0.2 Mn 0.3 O 2 as an active ingredient was added thereto, and 33,000 g of deionized water was added thereto.
  • the mixture was vigorously stirred at 330 rpm for 2 hours, and dried by spray drying to obtain a positive electrode composite active material of dried lanthanum hydroxide (Bi(OH) 3 ) coated with LiNi 0.5 Co 0.2 Mn 0.3 O 2 (based on the weight of the composite active material, The content of the additive was 7.8% by weight).
  • a lithium ion battery A29 was prepared according to the method of Example 1, except that the positive electrode composite active material of LiNi 0.5 Co 0.2 Mn 0.3 O 2 was coated with barium hydroxide (Sb(OH) 3 ) instead of aluminum hydroxide coated LiNi 0.5 Co.
  • a positive electrode composite active material of 0.2 Mn 0.3 O 2 wherein a positive electrode composite active material of lanthanum hydroxide (Sb(OH) 3 ) coated with LiNi 0.5 Co 0.2 Mn 0.3 O 2 is prepared as follows:
  • a lithium ion battery A30 was prepared according to the method of Example 1, except that a positive electrode composite active material coated with a boronic acid (B(OH) 3 ) LiNi 0.5 Co 0.2 Mn 0.3 O 2 was used instead of aluminum hydroxide coated LiNi 0.5 Co 0.2
  • a positive electrode composite active material of Mn 0.3 O 2 in which a positive electrode composite active material in which boric acid (B(OH) 3 ) is coated with LiNi 0.5 Co 0.2 Mn 0.3 O 2 is prepared as follows:
  • boric acid 618 g was added to 15000 g of deionized water to dissolve to prepare a boric acid solution, and 7305 g of a lithium nickel cobalt manganese oxide positive electrode material having a chemical formula of LiNi 0.5 Co 0.2 Mn 0.3 O 2 as an active ingredient was added thereto, and 10000 g of deionized water was added thereto, and the strength was 300 rpm. After stirring for 2 hours, the solution was spray-dried to obtain a dried boric acid (B(OH) 3 ) coated LiNi 0.5 Co 0.2 Mn 0.3 O 2 positive electrode composite active material (based on the weight of the composite active material, the additive content was 7.8) weight%).
  • B(OH) 3 dried boric acid coated LiNi 0.5 Co 0.2 Mn 0.3 O 2 positive electrode composite active material
  • a lithium ion battery A31 was prepared according to the method of Example 1, except that the positive electrode composite active material of LiNi 0.5 Co 0.2 Mn 0.3 O 2 was coated with barium hydroxide (Be(OH) 2 ) instead of aluminum hydroxide coated LiNi 0.5.
  • a positive electrode composite active material of Co 0.2 Mn 0.3 O 2 in which a positive electrode composite active material of lanthanum hydroxide (Be(OH) 2 ) coated with LiNi 0.5 Co 0.2 Mn 0.3 O 2 is prepared as follows:
  • the precursor was washed with deionized water to remove ammonium nitrate therein, and 5083 g of a lithium nickel cobalt manganese oxide positive electrode material having a chemical formula of LiNi 0.5 Co 0.2 Mn 0.3 O 2 as an active component was added thereto, and 7000 g of deionized water was added thereto to continue.
  • the mixture was vigorously stirred at 340 rpm for 2 hours, and the solution was spray-dried to obtain a dried positive electrode active material of lanthanum hydroxide (Be(OH) 2 ) coated with LiNi 0.5 Co 0.2 Mn 0.3 O 2 (based on the weight of the composite active material, the additive) The content is 7.8% by weight).
  • a lithium ion battery A32 was prepared according to the method of Example 1, except that a positive electrode composite active material coated with magnesium hydroxide (Mg(OH) 2 ) and LiNi 0.5 Co 0.2 Mn 0.3 O 2 was used instead of aluminum hydroxide to coat LiNi 0.5.
  • a positive electrode composite active material of Co 0.2 Mn 0.3 O 2 in which a positive electrode composite active material in which magnesium hydroxide (Mg(OH) 2 ) is coated with LiNi 0.5 Co 0.2 Mn 0.3 O 2 is prepared as follows:
  • magnesium nitrate hexahydrate 2560g was dissolved in 10000g of deionized water to prepare a magnesium nitrate solution. Under stirring, a mass fraction of 25% ammonia water was gradually added to the magnesium nitrate solution until the pH of the reaction system was 7.3, and the ammonia was controlled. The time was 2 hours, and after the completion of the reaction, magnesium hydroxide was precipitated.
  • the precursor was washed with deionized water to remove ammonium nitrate therein, and 6891 g of a lithium nickel cobalt manganese oxide positive electrode material having a chemical formula of LiNi 0.5 Co 0.2 Mn 0.3 O 2 as an active component was added thereto, and 9000 g of deionized water was added thereto to continue.
  • the mixture was vigorously stirred at 270 rpm for 2 hours, and the solution was spray-dried to obtain a dry magnesium hydroxide (Mg(OH) 2 ) coated LiNi 0.5 Co 0.2 Mn 0.3 O 2 positive electrode composite active material (based on the weight of the composite active material, the additive The content is 7.8% by weight).
  • a lithium ion battery A33 was prepared according to the method of Example 1, except that a positive electrode composite active material coated with copper hydroxide (Cu(OH) 2 ) was used to replace LiNi 0.5 with aluminum hydroxide coated with LiNi 0.5 Co 0.2 Mn 0.3 O 2 .
  • a positive electrode composite active material of Co 0.2 Mn 0.3 O 2 wherein a positive electrode composite active material in which copper hydroxide (Cu(OH) 2 ) is coated with LiNi 0.5 Co 0.2 Mn 0.3 O 2 is prepared as follows:
  • the precipitate was washed with deionized water to remove ammonium nitrate therefrom, and 11530 g of a lithium nickel cobalt manganese oxide positive electrode material having a chemical formula of LiNi 0.5 Co 0.2 Mn 0.3 O 2 as an active ingredient was added thereto, and 14,000 g of deionized water was added thereto, and 290 rpm was continued. After vigorously stirring for 2 hours, the solution was spray-dried to obtain a dried copper hydroxide (Cu(OH) 2 ) coated LiNi 0.5 Co 0.2 Mn 0.3 O 2 positive electrode composite active material (based on the weight of the composite active material, additive) The content is 7.8% by weight).
  • Cu(OH) 2 dried copper hydroxide
  • a lithium ion battery A34 was prepared according to the method of Example 1, except that a positive electrode composite active material coated with zinc hydroxide (Zn(OH) 2 ) and LiNi 0.5 Co 0.2 Mn 0.3 O 2 was used instead of aluminum hydroxide to coat LiNi 0.5.
  • a positive electrode composite active material of Co 0.2 Mn 0.3 O 2 wherein a positive electrode composite active material in which zinc hydroxide (Zn(OH) 2 ) is coated with LiNi 0.5 Co 0.2 Mn 0.3 O 2 is prepared as follows:
  • the precipitate was washed with deionized water to remove ammonium nitrate therein, and 11747 g of a lithium nickel cobalt manganese oxide positive electrode material having a chemical formula of LiNi 0.5 Co 0.2 Mn 0.3 O 2 as an active ingredient was added thereto, and 14,000 g of deionized water was added thereto, and the mixture was further heated at 360 rpm. After vigorously stirring for 2 hours, the solution was spray-dried to obtain a dry cathode active material of dry zinc hydroxide (Zn(OH) 2 ) coated with LiNi 0.5 Co 0.2 Mn 0.3 O 2 (based on the weight of the composite active material, additive) The content is about 7.8% by weight).
  • Zn(OH) 2 dry zinc hydroxide
  • a lithium ion battery D1 was prepared according to the method of Example 1, except that (1) LiNi 0.5 Co 0.2 Mn 0.3 O 2 lithium nickel cobalt manganese oxide cathode material was not surface-coated with an additive, and the battery positive electrode sheet was prepared without Surface-coated LiNi 0.5 Co 0.2 Mn 0.3 O 2 lithium nickel cobalt manganese oxide cathode material;
  • a lithium ion battery D2 was prepared according to the method of Example 2, except that (1) LiNi 0.8 Co 0.15 Al 0.05 O 2 lithium nickel cobalt aluminum oxide cathode material was not surface-coated with an additive, and the battery positive electrode sheet was prepared without Surface coated LiNi 0.8 Co 0.15 Al 0.05 O 2 lithium nickel cobalt aluminum oxide cathode material;
  • Lithium ion battery D3 was prepared according to the method of Example 3, except that (1) lithium cobaltate LiCoO 2 cathode material was not surface-coated with an additive, and the battery positive electrode sheet was prepared by using lithium cobalt oxide LiCoO which was not surface-coated. 2 cathode material;
  • the single cells (including the lithium ion batteries A1-A34 prepared in Examples 1-34 and the lithium ion batteries D1-D3 prepared in Comparative Examples 1-3) were charged at a current of 30 A to 8.5 V, and at 8.5 V. The constant pressure was maintained for 1 hour under voltage, and the phenomenon during the process was observed and recorded. Each of the 30 single cells was tested in parallel. The results are shown in Table 1.
  • the single cells (including the lithium ion batteries A1-A34 prepared in Examples 1-34 and the lithium ion batteries D1-D3 prepared in Comparative Examples 1-3) were charged at a current of 30 A to 4.25 V, and at 4.25 V. Constant voltage charging under voltage until the current is less than 1.5A. Extend the battery from the end face of the semi-cylindrical body with a radius of 75 mm from the direction perpendicular to the pole piece of the battery. The extrusion speed is 5 mm/s until the deformation of the battery reaches 30%. After the extrusion is completed, stay for one hour, observe and record. The phenomenon in the process. Each of the 30 single cells was tested in parallel. The results are shown in Table 2.
  • the single cells (including the lithium ion batteries A1-A34 prepared in Examples 1-34 and the lithium ion batteries D1-D3 prepared in Comparative Examples 1-3) were charged at a current of 30 A to 4.25 V, and at 4.25 V. Constant voltage charging under voltage until the current is less than 1.5A. Extend the battery from the end face of the semi-cylindrical body with a radius of 75 mm from the direction perpendicular to the pole piece of the battery. The extrusion speed is 5 mm/s until the deformation of the battery reaches 50%. After the extrusion is completed, it is allowed to stand for one hour, observe and record. The phenomenon in the process. Each of the 30 single cells was tested in parallel. The results are shown in Table 3.
  • the single cells (including the lithium ion batteries A1-A34 prepared in Examples 1-34 and the lithium ion batteries D1-D3 prepared in Comparative Examples 1-3) were charged at a current of 30 A to 4.25 V, and at 4.25 V. Constant voltage charging under voltage until the current is less than 1.5A.
  • a 6 mm diameter nail was passed through the battery at a rate of 25 mm/s in a direction perpendicular to the long and wide faces of the battery, and allowed to stand for one hour to observe and record the phenomenon during the process.
  • Each of the 30 single cells was tested in parallel. The results are shown in Table 4.
  • Example 1 Comparing the results of Example 1 and Examples 7-9 in Tables 1-4, it is understood that lithium ions having an additive content of 5.7-9.9 wt% based on the weight of the lithium ion battery composite active material are introduced in the preparation of the positive electrode or the negative electrode.
  • the battery composite active material can further improve the safety of the lithium ion battery thus prepared, and can further improve the safety of the prepared lithium ion battery under extremely severe conditions when the amount of the additive is further increased.

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Abstract

一种锂离子电池复合活性物质及其制备方法、锂离子电池电极浆料、正极或负极以及锂离子电池，涉及锂离子电池技术领域。该锂离子电池复合活性物质为添加剂包覆的活性物质，添加剂为M(OH) a，M为IIA族金属元素、IB族金属元素、IIB族金属元素、IIIB族金属元素、IVB族金属元素、VB族金属元素、VIB族金属元素、VIIB族金属元素、VIII族金属元素、IIIA族金属元素、IVA族金属元素、VA族金属元素、硼和硅中的至少一种元素，a＞0。将该锂离子电池复合活性物质作为正负极活性物质制备锂离子电池正极和/或负极，能够明显提高由此制备得到的锂离子电池的安全性。

Description

锂离子电池复合活性物质及其制备方法、锂离子电池电极浆料、正极或负极以及锂离子电池 技术领域
本发明涉及锂离子电池技术领域，具体地，涉及一种锂离子电池复合活性物质及其制备方法、一种锂离子电池电极浆料、一种正极或负极以及一种锂离子电池。
背景技术
锂离子电池是新一代的绿色高能电池，具有电压高、能量密度大、寿命长、自放电小、无记忆效应、工作温度范围宽等众多优点，在小型移动能源领域(例如手机、数码相机等)、大型移动能源领域(例如插电式混合动力车、纯电动车等)和固定能源领域(例如储能电站、UPS等)，都有着广泛的应用前景。
锂离子电池电压高也意味着在荷电状态下，电池的正、负极具有较大的电势差，也就意味着负极还原性更强，正极氧化性更强，热稳定性更差。特别是对于采用钴酸锂、锂镍钴铝氧、锂镍钴锰氧等高电压正极材料的电池而言，在过充、针刺、挤压等滥用情况下常常会因为热失控引起起火甚至爆炸，存在着严重的安全隐患。
除此之外，与采用不可燃且具有阻燃作用的水做电解液溶剂的传统的铅酸、碱性电池相比，商用锂离子电池通常采用可燃的碳酸酯类有机溶剂做电解液溶剂，或凝胶类聚合物做电解质，在滥用条件下，会进一步扩大安全事故的后果。
现有的锂离子电池的安全隐患阻碍了对锂离子电池的大规模应用，因此，研发一种安全性大幅提高的锂离子电池，具有重要的现实意义。
发明内容
本发明的目的是为了克服现有技术中锂离子电池安全性低、存在严重安全隐患的缺陷，提供一种锂离子电池复合活性物质及其制备方法、一种锂离子电池电极浆料、一种正极或负极以及一种锂离子电池。
为了实现上述目的，第一方面，本发明提供了一种锂离子电池复合活性物质，所述锂离子电池复合活性物质为添加剂包覆的活性物质，所述添加剂为M(OH)a，其中，M为IIA族金属元素、IB族金属元素、IIB族金属元素、IIIB族金属元素、IVB族金属元素、VB族金属元素、VIB族金属元素、VIIB族金属元素、VIII族金属元素、IIIA族金属元素、IVA族金属元素、VA族金属元素、硼和硅中的至少一种元素，a＞0。
第二方面，本发明提供了一种锂离子电池复合活性物质的制备方法，该方法包括：制备元素M的氢氧化物沉淀，在分散剂存在下，将所述元素M的氢氧化物沉淀与活性物质混合，然后将所得混合物进行热处理。
第三方面，本发明提供了一种锂离子电池电极浆料，所述电极浆料包括锂离子电池活性物质、粘结剂、导电剂、溶剂和任选的增稠剂，其中，所述锂离子电池活性物质为本发明所述的锂离子电池复合活性物质。
第四方面，本发明提供了一种锂离子电池正极或负极，所述锂离子电池正极或负极包括集流体及位于集流体上的电极敷料，所述电极敷料含有锂离子电池活性物质、粘结剂、导电剂和任选的增稠剂，其中，所述锂离子电池活性物质为本发明所述的锂离子电池复合活性物质。
第五方面，本发明提供了一种锂离子电池，所述锂离子电池包括电池壳体以及位于电池壳体内部的电芯组件和电解液，所述电芯组件包括正极、负极和隔膜，且所述正极为本发明所述的锂离子电池正极，和/或所述负极为本发明所述的锂离子电池负极。
本发明的发明人在研究中创造性发现，将本发明的锂离子电池复合活性物质(在活性物质的表面包覆本发明所述的添加剂，制备得到锂离子电池复合活性物质)作为正负极活性物质制备锂离子电池正极和/或负极，能够明显提高由此制备得到的锂离子电池的安全性，且几乎对锂离子电池的导电性能和循环性能等性能无不良影响。
本发明的其它特征和优点将在随后的具体实施方式部分予以详细说明。
具体实施方式
以下对本发明的具体实施方式进行详细说明。应当理解的是，此处所描述的具体实施方式仅用于说明和解释本发明，并不用于限制本发明。
在本文中所披露的范围的端点和任何值都不限于该精确的范围或值，这些范围或值应当理解为包含接近这些范围或值的值。对于数值范围来说，各个范围的端点值之间、各个范围的端点值和单独的点值之间，以及单独的点值之间可以彼此组合而得到一个或多个新的数值范围，这些数值范围应被视为在本文中具体公开。
第一方面，本发明提供了一种锂离子电池复合活性物质，所述锂离子电池复合活性物质为添加剂包覆的活性物质，所述添加剂为M(OH)a，其中，M为IIA族金属元素、IB族金属元素、IIB族金属元素、IIIB族金属元素、IVB族金属元素、VB族金属元素、VIB族金属元素、VIIB族金属元素、VIII族金属元素、IIIA族金属元素、IVA族金属元素、VA族金属元素、硼和硅中的至少一种元素，a＞0。
其中，本领域技术人员应该理解的是，M(OH)a中，a的选择符合相应物质的化学计量比原则。
本发明的锂离子电池复合活性物质中，优选情况下，添加剂中，所述IIA族金属元素为Be和/或Mg，所述IB族金属元素为Cu，所述IIB族金属元素为Zn，所述IIIB族金属元素为Y、Sc、La、Ce、Nd、Sm、Gd和Er中的至少一种，所述IVB族金属元素为Ti和/或Zr，所述VB族金属元素为V和/或Nb，所述VIB族金属元素为Cr和/或Mo，所述VIIB族金属元素为Mn，所述VIII族金属元素为Fe、Co和Ni中的至少一种，所述IIIA族金属元素为Al，所述IVA族金属元素为Sn，所述VA族金属元素为Bi和/或Sb。
本发明的锂离子电池复合活性物质中，本发明的发明人发现，在锂离子电池活性物质表面包覆特定的添加剂，能够得到安全性更好的锂离子电池活性物质，因此，为了进一步提高制备得到的锂离子电池的安全性，优选情况下，添加剂为氢氧化铝、原硅酸和氢氧化钛中的至少一种。
本发明的锂离子电池复合活性物质中，出于锂离子电池安全性提高和能量密度的综合考虑，优选情况下，以锂离子电池复合活性物质的重量为基准，添加剂的含量为0.05-30重量％，进一步优选为2-15.3重量％，更进一步优选为5.7-9.9重量％。
本发明的锂离子电池复合活性物质中，对于活性物质没有特别的限定，可以为本领域常规使用的各种活性物质，优选情况下，活性物质为正极活性物质或负极活性物质，所述正极活性物质为钴酸锂、锂镍氧、锂镍钴氧、锂镍钴铝氧、锂镍钴锰氧、锂镍锰氧、锰酸锂、钒酸锂、磷酸铁锂、磷酸锰锂、磷酸锰铁锂、磷酸锰铁镍锂、磷酸锰铁钴锂、磷酸锰铁镍钴锂、磷酸钒锂和硅酸铁锂中的至少一种，所述负极活性物质为石墨、钛酸锂、硅、硬碳、锡和氧化锡中的至少一种。
第二方面，本发明提供了上述的锂离子电池复合活性物质的制备方法，该方法包括：制备元素M的氢氧化物沉淀，在分散剂存在下，将所述元素M的氢氧化物沉淀与活性物质混合，然后将所得混合物进行热处理。
本发明的制备方法中，元素M的选择同上述添加剂中的元素M，可参见前述相应内容，在此不再重复赘述。
本发明的制备方法中，对于前述不同的元素M的氢氧化物沉淀的制备方法没有特别的限定，可以为本领域常用的各种方法，此为本领域技术人员所熟知，在此不再赘述。
本发明的制备方法中，本领域技术人员应该理解的是，在将元素M的氢氧化物沉淀与活性物质混合之前，先将制备得到的元素M的氢氧化物沉淀中残留的杂质除去，对于除去其中杂质的方法没有特别的限定，可以为本领域常用的各种方法，例如可以用去离子水洗涤以除去其中的杂质。
本发明的制备方法中，对于分散剂的种类没有特别的限定，可以为在制备元素M的氢氧化物沉淀的过程所用的溶剂，优选情况下，分散剂为异丙醇、去离子水、乙醇、丁醇和丙酮中的至少一种，进一步优选为异丙醇或去离子水。
本发明的制备方法中，优选情况下，将元素M的氢氧化物沉淀与活性物质混合的方式为强力搅拌，搅拌的条件优选包括：转速为100-400rpm，时间为1-10h。
本发明的制备方法中，对于热处理的方式没有特别的限定，可以为本领域常用的各种方式，优选情况下，热处理的方式为喷雾干燥、微波干燥、流化床干燥或烘箱干燥，为了提高效率，进一步优选为喷雾干燥。热处理的条件可以包括：温度为65-200℃，时间为1s-12h。其中，喷雾干燥的条件包括：温度为65-200℃，时间为1-100s，优选为1-10s。对于具体的温度和时间，可以根据不同的热处理方式进行选择，此为本领域技术人员所熟知，在此不再赘述。
根据本发明前述的制备方法，可以制备得到表面包覆有前述添加剂的活性物质，即得到锂离子电池复合活性物质，通过控制元素M的氢氧化物沉淀与活性物质的用量，可以制备得到特定添加剂含量的锂离子电池复合活性物质，优选情况下，控制元素M的氢氧化物沉淀与活性物质的用量，使得以锂离子电池复合活性物质的重量为基准，添加剂的含量为0.05-30重量％，进一步优选为2-15.3重量％，更进一步优选为5.7-9.9重量％。
第三方面，本发明提供了一种锂离子电池电极浆料，所述电极浆料包括锂离子电池活性物质、粘结剂、导电剂、溶剂和任选的增稠剂，其中，所述锂离子电池活性物质为本发明所述的锂离子电池复合活性物质。
其中，本领域技术人员应该理解的是，本发明所述的锂离子电池电极浆料可以为锂离子电池正极浆料，也可以为锂离子电池负极浆料。在锂离子电池正极浆料或锂离子电池负极浆料中，对于活性物质、粘结剂、导电剂、溶剂和增稠剂的种类选择和用量没有特别的限定，可以分别为本领域相应组分的常规的种类选择和用量，出于电池能量密度和电池综合性能的考虑，优选情况下，以所述锂离子电池复合活性物质的重量为基准，粘结剂以干基计的含量为0.5-5重量％，导电剂的含量为0.5-5重量％，溶剂的含量为55-200重量％，增稠剂的含量为0-2.5重量％。其中，增稠剂一般在锂离电池正极浆料中不使用，而在锂离子电池负极浆料中使用，以所述锂离子电池复合活性物质的重量为基准，含量为0.5-2.5重量％。
其中，锂离子电池正极浆料中，对于锂离子电池复合活性物质中的正极活性物质没有特别的限定，可以为如前文所述的各种正极活性物质，在此不再重复赘述。
其中，锂离子电池负极浆料中，对于锂离子电池复合活性物质中的负极活性物质没有特别的限定，可以为如前文所述的各种负极活性物质，在此不再重复赘述。
锂离子电池正极浆料和锂离子电池负极浆料中，对于粘结剂没有特别的限定，可以为本领域常规使用的各种粘结剂，优选情况下，粘结剂为聚丙烯酰胺、聚偏二氟乙烯、聚四氟乙烯、丁苯橡胶、纤维素基聚合物、聚乙烯醇、聚烯烃、氟化橡胶和聚胺酯中的至少一种，纤维素基聚合物可以选自甲基纤维素、乙基纤维素、羟丙基甲基纤维素和羟丙基乙基纤维素中的一种或几种。前述粘结剂为聚合物时，各聚合物的数均分子量一般 为30-150万。
锂离子电池正极浆料和锂离子电池负极浆料中，对于导电剂没有特别的限定，可以为本领域常规使用的各种导电剂，优选情况下，导电剂为科琴黑、乙炔黑、石墨烯、碳纳米管、碳纤维(VGCF)、微晶石墨和导电碳黑(Super-P)中的至少一种。
其中，对于溶剂没有特别的限定，可以为本领域常规使用的各种溶剂，优选情况下，溶剂为N-甲基吡咯烷酮(NMP)、去离子水、四氢呋喃、二甲基亚砜、乙醇和异丙醇中的至少一种。其中，进一步优选地，在锂离子电池正极浆料中，溶剂为N-甲基吡咯烷酮；在锂离子电池负极浆料中，溶剂为去离子水和/或N-甲基吡咯烷酮。
其中，增稠剂多应用于锂离子电池负极浆料中，在锂离子电池正极浆料中是否添加增稠剂可以根据实际应用情况进行选择，具体选择为本领域技术人员所熟知，优选情况下，增稠剂为羧甲基纤维素钠(CMC)、聚乙烯吡咯烷酮、聚乙二醇和聚乙烯醇中的至少一种。
其中，对于本发明的锂离子电池电极浆料的制备方法没有特别的限定，可以为本领域常用的各种方法，只要能够将含有前述组分的浆料混合均匀即可，例如，含有锂离子电池复合活性物质、粘结剂、导电剂、溶剂和任选的增稠剂的浆料可以通过先将粘结剂和溶剂混合，得到混合液，然后将锂离子电池复合活性物质、导电剂和任选的增稠剂与混合液进行混合，或者可以通过将增稠剂或粘结剂和溶剂混合，得到混合液，然后将锂离子电池复合活性物质、导电剂和粘结剂或增稠剂与混合液进行混合。
第四方面，本发明提供了一种锂离子电池正极或负极，所述锂离子电池正极或负极包括集流体及位于集流体上的电极敷料，所述电极敷料含有锂离子电池活性物质、粘结剂、导电剂和任选的增稠剂，其中，所述锂离子电池活性物质为本发明所述的锂离子电池复合活性物质。
本发明的锂离子电池正极或负极中，对于活性物质、粘结剂、导电剂、增稠剂的具体选择，可以参见前文相应描述，在此不再重复赘述。
本发明的锂离子电池正极或负极中，为了进一步提高制备得到的锂离子电池的安全性同时兼顾电池能量密度和电池综合性能，以电极敷料的干重为基准，添加剂的含量为0.05-25重量％，进一步优选为2-14重量％，更优选为5-9重量％。本领域技术人员应该理解的是，电极敷料的干重是指涂覆在集流体上的所有浆料烘干后得到的物质的重量。
其中，对于制备锂离子电池正极或负极的方法没有特别的限定，可以为本领域常用的各种方法，例如可以包括：将本发明所述的锂离子电池电极浆料涂覆在集流体上，烘干。
其中，锂离子电池正极中，对于集流体没有特别的限定，可以为本领域常用的各种正极集流体，例如正极集流体可以为铝箔。
其中，锂离子电池负极中，对于集流体没有特别的限定，可以为本领域常用的各种负极集流体，例如负极集流体可以为铜箔。
其中，对于涂覆的方法没有特别的限定，可以为本领域常用的各种方法，此为本领域技术人所熟知，在此不再赘述。
其中，对于烘干的方法没有特别的限定，可以为本领域常用的各种方法，优选情况下，烘干的条件包括：温度为80-180℃。
第五方面，本发明提供了一种锂离子电池，所述锂离子电池包括电池壳体以及位于电池壳体内部的电芯组件和电解液，所述电芯组件包括正极、负极和隔膜，且所述正极为本发明所述的锂离子电池正极，和/或所述负极为本发明所述的锂离子电池负极。
本发明的锂离子电池中，本领域技术人员应该理解的是，正极和负极中的至少一个电极为由本发明所述的锂离子电池复合活性物质制备得到的正极或负极，即，正极为本 发明所述的锂离子电池正极，或者负极为本发明所述的锂离子电池负极，或者，正极和负极同时分别为本发明所述的锂离子电池正极和负极。
本发明的锂离子电池中，形成锂离子电池的隔膜和电解液可以为本领域常规使用的隔膜和非水电解液。
其中，隔膜设置于正极和负极之间，它具有电绝缘性能和液体保持性能，并使电芯组件和非水电解液一起容纳在电池壳中。隔膜可以为本领域常用的各种隔膜，如高分子聚合物微孔薄膜，包括聚丙稀微孔薄膜和聚丙稀与聚乙烯的多层复合微孔薄膜。隔膜的位置、性质和种类为本领域技术人员所熟知，在此不再赘述。
其中，非水电解液为电解质锂盐和非水溶剂的混合溶液，对它没有特别限定，可以使用本领域常规的非水电解液。比如电解质锂盐选自六氟磷酸锂(LiPF6)、高氯酸锂、四氟硼酸锂、六氟砷酸锂、卤化锂、氯铝酸锂及氟烃基磺酸锂中的一种或几种。非水溶剂选用链状酸酯和环状酸酯混合溶液，其中链状酸酯可以为碳酸二甲酯(DMC)、碳酸二乙酯(DEC)、碳酸甲乙酯(EMC)、碳酸甲丙酯(MPC)、碳酸二丙酯(DPC)以及其它含氟、含硫或含不饱和键的链状有机酯类中的至少一种，环状酸酯可以为碳酸乙烯酯(EC)、碳酸丙烯酯(PC)、碳酸亚乙烯酯(VC)、γ-丁内酯(γ-BL)、磺内酯以及其它含氟、含硫或含不饱和键的环状有机酯类中的至少一种。电解液的注入量一般为5-8克/安时，电解液的浓度一般为0.8-1.2摩尔/升。
本发明的锂离子电池中，对于电池壳体没有特别的限定，可以为本领域常用的各种电池壳体，此为本领域技术人员所熟知，在此不再赘述。
本发明的锂离子电池中，制备电池的方法为本领域的常用方法，一般来说，将正极和负极与隔膜构成一个电芯组件，将得到的电芯组件和非水电解液密封在电池壳中，即可得到锂离子电池。具体方法为本领域技术人员所熟知，在此不再赘述。
实施例
以下将通过实施例对本发明进行详细描述，但并不因此限制本发明，如无特别说明，所用的材料均可通过商购获得，所用的方法均为本领域的常规方法。
锂镍钴锰氧LiNi0.5Co0.2Mn0.3O2购自上海杉杉科技有限公司。
钴酸锂LiCoO2购自天津巴莫科技股份有限公司。
锂镍钴铝氧LiNi0.8Co0.15Al0.05O2购自日本户田工业株式会社。
Pvdf粘结剂HSV900购自法国阿科玛公司。
PTFE乳液粘结剂D210固含量为60％，购自日本大金工业株式会社。
导电剂Super-P购自瑞士特密高公司。
天然石墨购自深圳贝特瑞新能源材料股份有限公司。
增稠剂CMC购自日本第一工业制药株式会社。
丁苯橡胶乳胶粘结剂固含量为50％，购自日本瑞翁株式会社。
实施例1
a.表面包覆氢氧化铝添加剂的复合活性物质的制备
将3750g九水硝酸铝溶解在10000g去离子水中，制得硝酸铝溶液，在搅拌条件下，向硝酸铝溶液中逐步加入质量分数为25％的氨水，直至反应体系pH值为7.3，控制加氨水时间为2小时，反应结束后得到氢氧化铝沉淀。将该沉淀用去离子水洗涤以去除其中的硝酸铵，并用异丙醇置换水，将作为活性成分的9220g化学式为LiNi0.5Co0.2Mn0.3O2的锂镍钴锰氧正极材料加入沉淀中，加入12000g异丙醇，300rpm下强力搅拌2小时，喷雾干燥，得到氢氧化铝(Al(OH)3)包覆LiNi0.5Co0.2Mn0.3O2的正极复合活性物质(以复合活性物质的重量为基准，添加剂的含量为7.8重量％)。
b.单体电池的制作
(1)电池正极极片制备
将23875g上述制备得到的正极复合活性物质、500g粘结剂HSV900、625g导电剂Super-P混合，具体方法为：先以25000g NMP为溶剂，将粘结剂HSV900溶解，并在搅拌下分别将正极复合活性物质、导电剂Super-P与上述粘结剂的溶液混合，之后搅拌形成均匀的正极浆料；
将该正极浆料均匀涂覆在厚度为25μm的铝箔上，涂覆宽度为160mm，敷料双面面密度为331.4g/m2(敷料双面面密度以烘干后的重量计，下同，且以电极敷料的干重为基准，添加剂的含量约为7.5重量％)，然后在110℃下烘干，得到正极极片。
(2)电池负极极片制备
将12220g天然石墨负极材料、175g增稠剂CMC、215g导电剂Super-P和780g丁苯橡胶乳胶粘结剂混合，具体方法为：先以12500g去离子水为溶剂，将增稠剂CMC溶解，并在搅拌下分别将丁苯橡胶乳胶粘结剂、导电剂Super-P、天然石墨负极材料与上述增稠剂的溶液混合，之后搅拌形成均匀的负极浆料；
将该负极浆料均匀涂覆在厚度为18μm的铜箔上，涂覆宽度为164mm，敷料双面面密度为165g/m2(以烘干后的重量计，下同)，然后在100℃下烘干，得到负极极片。
(3)单体电池的装配
将正极极片裁剪成120mm×160mm的尺寸作为正极，将负极极片裁剪成125mm×164mm的尺寸作为负极，以聚丙烯膜为隔膜，组装成电芯组件，放入软包铝塑膜电池壳体中，并将正负极极耳分别与铝塑膜焊接在一起，过程中保证极耳与电池壳体的绝缘，经过核算，正极材料中活性成分锂镍钴锰氧的重量约为191g，负极活性物质天然石墨的重量约为104g，电池的标称容量为30Ah。随后将LiPF6按1摩尔/升的浓度溶解在EC/DMC＝1:1(体积比)的混合溶剂中形成非水电解液，在氮气气氛保护下将160g此电解液注入上述电池半成品中，并将电池封口。将该电池在45℃的条件下陈化48小时，之后以0.6A的电流充电至4.00V，再在45℃的条件下二次陈化48小时，最后在氮气气氛保护下将电池中产生的气体抽出并将电池二次封口，得到锂离子电池A1。
实施例2
按照实施例1的方法制备锂离子电池A2，不同的是，用原硅酸(Si(OH)4)包覆LiNi0.80Co0.15Al0.05O2的正极复合活性物质代替氢氧化铝包覆LiNi0.5Co0.2Mn0.3O2的正极复合活性物质，其中，原硅酸(Si(OH)4)包覆LiNi0.80Co0.15Al0.05O2的正极复合活性物质按如下方法制备：
将2120g五水偏硅酸钠加入20000g去离子水中搅拌溶解，得到偏硅酸钠溶液。在280rpm强力搅拌下，向偏硅酸钠溶液中快速加入15重量％的稀硝酸，直至反应体系pH值为7.3，反应结束后得到原硅酸(氢氧化硅)沉淀。将该沉淀用去离子水洗涤以去除其中的硝酸钠，并用异丙醇置换水，将作为活性成分的11348g化学式为LiNi0.80Co0.15Al0.05O2的锂镍钴铝氧正极材料加入沉淀中，加入14000g异丙醇，继续310rpm下强力搅拌2小时，喷雾干燥，得到原硅酸(Si(OH)4)包覆LiNi0.80Co0.15Al0.05O2的正极复合活性物质(以复合活性物质的重量为基准，添加剂的含量为7.8重量％)。
实施例3
按照实施例1的方法制备锂离子电池A3，不同的是，用氢氧化钛(Ti(OH)4)包覆钴酸锂的正极复合活性物质代替氢氧化铝包覆LiNi0.5Co0.2Mn0.3O2的正极复合活性物质，其中，氢氧化钛(Ti(OH)4)包覆钴酸锂的正极复合活性物质质按如下方法制备：
将1600g氢氧化钠加入20000g去离子水中溶解，得到氢氧化钠溶液，在0℃水浴、 240rpm强力搅拌的条件下，将1900g四氯化钛液体缓慢加入氢氧化钠溶液中，控制加四氯化钛时间为3小时，反应结束后得到氢氧化钛沉淀。将该沉淀用去离子水洗涤以去除其中的氯化钠，并加入异丙醇置换水，将作为活性成分的13712g化学式为LiCoO2的钴酸锂正极材料加入沉淀中，加入16000g异丙醇，继续360rpm下强力搅拌2小时，喷雾干燥，得到氢氧化钛(Ti(OH)4)包覆钴酸锂的正极复合活性物质(以复合活性物质的重量为基准，添加剂的含量为7.8重量％)。
实施例4
按照实施例1的方法制备锂离子电池A4，不同的是，(1)LiNi0.5Co0.2Mn0.3O2锂镍钴锰氧正极材料未用添加剂进行表面包覆，电池正极极片制备采用未进行表面包覆的LiNi0.5Co0.2Mn0.3O2锂镍钴锰氧正极材料，且在电池正极极片制备时，敷料双面面密度为305.5g/m2；(2)电池负极极片制备的方法如下：
将3750g九水硝酸铝溶解在10000g去离子水中，制得硝酸铝溶液，在搅拌条件下，向硝酸铝溶液中逐步加入质量分数为25％的氨水，直至反应体系pH值为7.3，控制加氨水时间为2小时，反应结束后得到氢氧化铝沉淀。将该沉淀用去离子水洗涤以去除其中的硝酸铵，用异丙醇置换水，将作为活性成分的9220g天然石墨负极材料加入沉淀中，加入12000g异丙醇，继续330rpm下强力搅拌2小时，喷雾干燥，得到氢氧化铝(Al(OH)3)包覆天然石墨的负极复合活性物质(以复合活性物质的重量为基准，添加剂的含量为7.8重量％)。
将12220g氢氧化铝(Al(OH)3)包覆天然石墨的负极复合活性物质、175g增稠剂CMC、215g导电剂Super-P和780g丁苯橡胶乳胶粘结剂混合，具体方法为：先以12500g去离子水为溶剂，将增稠剂CMC溶解，并在搅拌下分别将丁苯橡胶乳胶粘结剂、导电剂Super-P、负极复合活性物质与上述增稠剂的溶液混合，之后搅拌形成均匀的负极浆料；
将该负极浆料均匀涂覆在厚度为18μm的铜箔上，涂覆宽度为164mm，敷料双面面密度为179g/m2，然后在100℃下烘干，得到负极极片。
实施例5
按照实施例1的方法制备锂离子电池A5，不同的是，(1)表面包覆氢氧化铝添加剂的正极复合活性物质按如下方法制备：
将3750g九水硝酸铝溶解在10000g去离子水中，制得硝酸铝溶液，在搅拌条件下，向硝酸铝溶液中逐步加入质量分数为25％的氨水，直至反应体系pH值为7.3，控制加氨水时间为2小时，反应结束后得到氢氧化铝沉淀。将该沉淀用去离子水洗涤以去除其中的硝酸铵，用异丙醇置换水，将作为活性成分的12904g化学式为LiNi0.5Co0.2Mn0.3O2的锂镍钴锰氧正极材料加入沉淀中，加入15000g异丙醇，320rpm强力搅拌2小时，喷雾干燥，得到氢氧化铝(Al(OH)3)包覆LiNi0.5Co0.2Mn0.3O2的正极复合活性物质(以复合活性物质的重量为基准，添加剂的含量为5.7重量％)。
(2)电池正极极片制备时，正极敷料双面面密度调整为324g/m2(电池中正极活性成分锂镍钴锰氧的重量与实施例1相同)。
实施例6
按照实施例1的方法制备锂离子电池A6，不同的是，(1)表面包覆氢氧化铝添加剂的正极复合活性物质按如下方法制备：
将3750g九水硝酸铝溶解在10000g去离子水中，制得硝酸铝溶液，在搅拌条件下，向硝酸铝溶液中逐步加入质量分数为25％的氨水，直至反应体系pH值为7.3，控制加 氨水时间为2小时，反应结束后得到氢氧化铝沉淀。将该沉淀用去离子水洗涤以去除其中的硝酸铵，用异丙醇置换水，将作为活性成分的7099g化学式为LiNi0.5Co0.2Mn0.3O2的锂镍钴锰氧正极材料加入沉淀中，加入9000g异丙醇，230rpm强力搅拌2小时，喷雾干燥，得到氢氧化铝(Al(OH)3)包覆LiNi0.5Co0.2Mn0.3O2的正极复合活性物质(以复合活性物质的重量为基准，添加剂的含量为9.9重量％)。
(2)电池正极极片制备时，正极敷料双面面密度调整为339.1g/m2(电池中正极活性成分锂镍钴锰氧的重量与实施例1相同)。
实施例7
按照实施例1的方法制备锂离子电池A7，不同的是，(1)表面包覆氢氧化铝添加剂的正极复合活性物质按如下方法制备：
将3750g九水硝酸铝溶解在10000g去离子水中，制得硝酸铝溶液，在搅拌条件下，向硝酸铝溶液中逐步加入质量分数为25％的氨水，直至反应体系pH值为7.3，控制加氨水时间为2小时，反应结束后得到氢氧化铝沉淀。将该沉淀用去离子水洗涤以去除其中的硝酸铵，用异丙醇置换水，将作为活性成分的38220g化学式为LiNi0.5Co0.2Mn0.3O2的锂镍钴锰氧正极材料加入沉淀中，加入40000g异丙醇，继续270rpm强力搅拌2小时，喷雾干燥，得到氢氧化铝(Al(OH)3)包覆LiNi0.5Co0.2Mn0.3O2的正极复合活性物质(以复合活性物质的重量为基准，添加剂的含量为2重量％)。
(2)电池正极极片制备时，正极敷料双面面密度调整为311.8g/m2(电池中正极活性成分锂镍钴锰氧的重量与实施例1相同)。
实施例8
按照实施例1的方法制备锂离子电池A8，不同的是，(1)表面包覆氢氧化铝添加剂的正极复合活性物质按如下方法制备：
将3750g九水硝酸铝溶解在10000g去离子水中，制得硝酸铝溶液，在搅拌条件下，向硝酸铝溶液中逐步加入质量分数为25％的氨水，直至反应体系pH值为7.3，控制加氨水时间为2小时，反应结束后得到氢氧化铝沉淀。将该沉淀用去离子水洗涤以去除其中的硝酸铵，用异丙醇置换水，将作为活性成分的85887g化学式为LiNi0.5Co0.2Mn0.3O2的锂镍钴锰氧正极材料加入沉淀中，加入88000g异丙醇，继续350rpm强力搅拌2小时，喷雾干燥，得到氢氧化铝(Al(OH)3)包覆LiNi0.5Co0.2Mn0.3O2的正极复合活性物质(以复合活性物质的重量为基准，添加剂的含量为0.9重量％)。
(2)电池正极极片制备时，正极敷料双面面密度调整为308.3g/m2(电池中正极活性成分锂镍钴锰氧的重量与实施例1相同)。
实施例9
按照实施例1的方法制备锂离子电池A9，不同的是，(1)表面包覆氢氧化铝添加剂的正极复合活性物质按如下方法制备：
将3750g九水硝酸铝溶解在10000g去离子水中，制得硝酸铝溶液，在搅拌条件下，向硝酸铝溶液中逐步加入质量分数为25％的氨水，直至反应体系pH值为7.3，控制加氨水时间为2小时，反应结束后得到氢氧化铝沉淀。将该沉淀用去离子水洗涤以去除其中的硝酸铵，用异丙醇置换水，将作为活性成分的4599g化学式为LiNi0.5Co0.2Mn0.3O2的锂镍钴锰氧正极材料加入沉淀中，加入7000g异丙醇，继续270rpm强力搅拌2小时，喷雾干燥，得到氢氧化铝(Al(OH)3)包覆LiNi0.5Co0.2Mn0.3O2的正极复合活性物质(以复合活性物质的重量为基准，添加剂的含量为14.5重量％)。
(2)电池正极极片制备时，正极敷料双面面密度调整为357.4g/m2(电池中正极活 性成分锂镍钴锰氧的重量与实施例1相同)。
实施例10
按照实施例1的方法制备锂离子电池A10，不同的是，用氢氧化钇(Y(OH)3)包覆LiNi0.5Co0.2Mn0.3O2的正极复合活性物质代替氢氧化铝包覆LiNi0.5Co0.2Mn0.3O2的正极复合活性物质，其中，氢氧化钇(Y(OH)3)包覆LiNi0.5Co0.2Mn0.3O2的正极复合活性物质按如下方法制备：
将3830g六水硝酸钇溶解在10000g去离子水中，制得硝酸钇溶液，在搅拌条件下，向硝酸钇溶液中逐步加入质量分数为25％的氨水，直至反应体系pH值为7.3，控制加氨水时间为2小时，反应结束后得到氢氧化钇沉淀。将该沉淀用去离子水洗涤以去除其中的硝酸铵，将作为活性成分的16537g化学式为LiNi0.5Co0.2Mn0.3O2的锂镍钴锰氧正极材料加入沉淀中，加入19000g水，继续360rpm强力搅拌2小时，最后通过喷雾干燥得到干燥的氢氧化钇(Y(OH)3)包覆LiNi0.5Co0.2Mn0.3O2的正极复合活性物质(以复合活性物质的重量为基准，添加剂的含量为7.8重量％)。
实施例11
按照实施例1的方法制备锂离子电池A11，不同的是，用氢氧化钪(Sc(OH)3)包覆LiNi0.5Co0.2Mn0.3O2的正极复合活性物质代替氢氧化铝包覆LiNi0.5Co0.2Mn0.3O2的正极复合活性物质，其中，氢氧化钪(Sc(OH)3)包覆LiNi0.5Co0.2Mn0.3O2的正极复合活性物质按如下方法制备：
将3390g六水硝酸钪溶解在10000g去离子水中，制得硝酸钪溶液，在搅拌条件下，向硝酸钪溶液中逐步加入质量分数为25％的氨水，直至反应体系pH值为7.3，控制加氨水时间为2小时，反应结束后得到氢氧化钪沉淀。将该沉淀用去离子水洗涤以去除其中的硝酸铵，将作为活性成分的11348g化学式为LiNi0.5Co0.2Mn0.3O2的锂镍钴锰氧正极材料加入沉淀中，加入14000g水，继续290rpm强力搅拌2小时，最后通过喷雾干燥得到干燥的氢氧化钪(Sc(OH)3)包覆LiNi0.5Co0.2Mn0.3O2的正极复合活性物质(以复合活性物质的重量为基准，添加剂的含量为7.8重量％)。
实施例12
按照实施例1的方法制备锂离子电池A12，不同的是，用氢氧化锆(Zr(OH)4)包覆LiNi0.5Co0.2Mn0.3O2的正极复合活性物质代替氢氧化铝包覆LiNi0.5Co0.2Mn0.3O2的正极复合活性物质，其中，氢氧化锆(Zr(OH)4)包覆LiNi0.5Co0.2Mn0.3O2的正极复合活性物质按如下方法制备：
将1600g氢氧化钠加入20000g去离子水中溶解，得到氢氧化钠溶液，在0℃水浴、220rpm强力搅拌的条件下，将2330g四氯化锆粉末缓慢加入氢氧化钠溶液中，控制加四氯化锆粉末时间为2小时，反应结束后得到氢氧化锆沉淀。将该沉淀用去离子水洗涤以去除其中的氯化钠，并加入异丙醇置换水，将作为活性成分的18795g化学式为LiNi0.5Co0.2Mn0.3O2的锂镍钴锰氧正极材料加入沉淀中，加入21000g异丙醇，继续350rpm强力搅拌2小时，最后通过喷雾干燥得到干燥的氢氧化锆(Zr(OH)4)包覆LiNi0.5Co0.2Mn0.3O2的正极复合活性物质(以复合活性物质的重量为基准，添加剂的含量为7.8重量％)。
实施例13
按照实施例1的方法制备锂离子电池A13，不同的是，用氢氧化钒(V(OH)3)包覆LiNi0.5Co0.2Mn0.3O2的正极复合活性物质代替氢氧化铝包覆LiNi0.5Co0.2Mn0.3O2的正极复 合活性物质，其中，氢氧化钒(V(OH)3)包覆LiNi0.5Co0.2Mn0.3O2的正极复合活性物质按如下方法制备：
将1200g氢氧化钠加入20000g去离子水中溶解，得到氢氧化钠溶液，在0℃水浴、氮气保护、且260rpm强力搅拌的条件下，将1570g三氯化钒粉末缓慢加入氢氧化钠溶液中，控制加三氯化钒粉末时间为2小时，反应结束后得到氢氧化钒沉淀。在氮气保护下，将该沉淀用去离子水洗涤以去除其中的氯化钠，并加入异丙醇置换水，将作为活性成分的12045g化学式为LiNi0.5Co0.2Mn0.3O2的锂镍钴锰氧正极材料加入其中，加入14000g异丙醇，继续270rpm下强力搅拌2小时，最后通过喷雾干燥得到干燥的氢氧化钒(V(OH)3)包覆LiNi0.5Co0.2Mn0.3O2的正极复合活性物质(以复合活性物质的重量为基准，添加剂的含量为7.8重量％)。
实施例14
按照实施例1的方法制备锂离子电池A14，不同的是，用氢氧化镧(La(OH)3)包覆LiNi0.5Co0.2Mn0.3O2的正极复合活性物质代替氢氧化铝包覆LiNi0.5Co0.2Mn0.3O2的正极复合活性物质，其中，氢氧化镧(La(OH)3)包覆LiNi0.5Co0.2Mn0.3O2的正极复合活性物质按如下方法制备：
将4330g六水硝酸镧溶解在20000g去离子水中，制得硝酸镧溶液，在搅拌条件下，向硝酸镧溶液中逐步加入质量分数为25％的氨水，直至反应体系pH值为7.3，控制加氨水时间为2小时，反应结束后得到氢氧化镧沉淀。将该沉淀用去离子水洗涤以去除其中的硝酸铵，将作为活性成分的22447g化学式为LiNi0.5Co0.2Mn0.3O2的锂镍钴锰氧正极材料加入其中，加入25000g去离子水，继续300rpm强力搅拌2小时，最后通过喷雾干燥得到干燥的氢氧化镧(La(OH)3)包覆LiNi0.5Co0.2Mn0.3O2的正极复合活性物质(以复合活性物质的重量为基准，添加剂的含量为7.8重量％)。
实施例15
按照实施例1的方法制备锂离子电池A15，不同的是，用氢氧化铈(Ce(OH)3)包覆LiNi0.5Co0.2Mn0.3O2的正极复合活性物质代替氢氧化铝包覆LiNi0.5Co0.2Mn0.3O2的正极复合活性物质，其中，氢氧化铈(Ce(OH)3)包覆LiNi0.5Co0.2Mn0.3O2的正极复合活性物质按如下方法制备：
将4340g六水硝酸铈溶解在15000g去离子水中，制得硝酸铈溶液，在搅拌条件下，向硝酸铈溶液中逐步加入质量分数为25％的氨水，直至反应体系pH值为7.3，控制加氨水时间为2小时，反应结束后得到氢氧化铈沉淀。将该沉淀用去离子水洗涤以去除其中的硝酸铵，将作为活性成分的22589g化学式为LiNi0.5Co0.2Mn0.3O2的锂镍钴锰氧正极材料加入其中，加入25000g去离子水，继续330rpm强力搅拌2小时，最后通过喷雾干燥得到干燥的氢氧化铈(Ce(OH)3)包覆LiNi0.5Co0.2Mn0.3O2的正极复合活性物质(以复合活性物质的重量为基准，添加剂的含量为7.8重量％)。
实施例16
按照实施例1的方法制备锂离子电池A16，不同的是，用氢氧化钕(Nd(OH)3)包覆LiNi0.5Co0.2Mn0.3O2的正极复合活性物质代替氢氧化铝包覆LiNi0.5Co0.2Mn0.3O2的正极复合活性物质，其中，氢氧化钕(Nd(OH)3)包覆LiNi0.5Co0.2Mn0.3O2的正极复合活性物质按如下方法制备：
将4380g六水硝酸钕溶解在15000g去离子水中，制得硝酸钕溶液，在搅拌条件下，向硝酸钕溶液中逐步加入质量分数为25％的氨水，直至反应体系pH值为7.3，控制加 氨水时间为2小时，反应结束后得到氢氧化钕沉淀。将该沉淀用去离子水洗涤以去除其中的硝酸铵，将作为活性成分的23074g化学式为LiNi0.5Co0.2Mn0.3O2的锂镍钴锰氧正极材料加入其中，加入25000g去离子水，继续330rpm强力搅拌2小时，最后通过喷雾干燥得到干燥的氢氧化钕(Nd(OH)3)包覆LiNi0.5Co0.2Mn0.3O2的正极复合活性物质(以复合活性物质的重量为基准，添加剂的含量为7.8重量％)。
实施例17
按照实施例1的方法制备锂离子电池A17，不同的是，用氢氧化钐(Sm(OH)3)包覆LiNi0.5Co0.2Mn0.3O2的正极复合活性物质代替氢氧化铝包覆LiNi0.5Co0.2Mn0.3O2的正极复合活性物质，其中，氢氧化钐(Sm(OH)3)包覆LiNi0.5Co0.2Mn0.3O2的正极复合活性物质按如下方法制备：
将4440g六水硝酸钐溶解在15000g去离子水中，制得硝酸钐溶液，在搅拌条件下，向硝酸钐溶液中逐步加入质量分数为25％的氨水，直至反应体系pH值为7.3，控制加氨水时间为2小时，反应结束后得到氢氧化钐沉淀。将该沉淀用去离子水洗涤以去除其中的硝酸铵，将作为活性成分的23807g化学式为LiNi0.5Co0.2Mn0.3O2的锂镍钴锰氧正极材料加入其中，加入26000g去离子水，继续340rpm强力搅拌2小时，最后通过喷雾干燥得到干燥的氢氧化钐(Sm(OH)3)包覆LiNi0.5Co0.2Mn0.3O2的正极复合活性物质(以复合活性物质的重量为基准，添加剂的含量为7.8重量％)。
实施例18
按照实施例1的方法制备锂离子电池A18，不同的是，用氢氧化钆(Gd(OH)3)包覆LiNi0.5Co0.2Mn0.3O2的正极复合活性物质代替氢氧化铝包覆LiNi0.5Co0.2Mn0.3O2的正极复合活性物质，其中，氢氧化钆(Gd(OH)3)包覆LiNi0.5Co0.2Mn0.3O2的正极复合活性物质按如下方法制备：
将4510g六水硝酸钆溶解在15000g去离子水中，制得硝酸钆溶液，在搅拌条件下，向硝酸钆溶液中逐步加入质量分数为25％的氨水，直至反应体系pH值为7.3，控制加氨水时间为2小时，反应结束后得到氢氧化钆沉淀。将该沉淀用去离子水洗涤以去除其中的硝酸铵，将作为活性成分的24622g化学式为LiNi0.5Co0.2Mn0.3O2的锂镍钴锰氧正极材料加入其中，加入27000g去离子水，继续290rpm强力搅拌2小时，最后通过喷雾干燥得到干燥的氢氧化钆(Gd(OH)3)包覆LiNi0.5Co0.2Mn0.3O2的正极复合活性物质(以复合活性物质的重量为基准，添加剂的含量为7.8重量％)。
实施例19
按照实施例1的方法制备锂离子电池A19，不同的是，用氢氧化铒(Er(OH)3)包覆LiNi0.5Co0.2Mn0.3O2的正极复合活性物质代替氢氧化铝包覆LiNi0.5Co0.2Mn0.3O2的正极复合活性物质，其中，氢氧化铒(Er(OH)3)包覆LiNi0.5Co0.2Mn0.3O2的正极复合活性物质按如下方法制备：
将4433g五水硝酸铒溶解在15000g去离子水中，制得硝酸铒溶液，在搅拌条件下，向硝酸铒溶液中逐步加入质量分数为25％的氨水，直至反应体系pH值为7.3，控制加氨水时间为2小时，反应结束后得到氢氧化铒沉淀。将该沉淀用去离子水洗涤以去除其中的硝酸铵，将作为活性成分的25804g化学式为LiNi0.5Co0.2Mn0.3O2的锂镍钴锰氧正极材料加入其中，加入28000g去离子水，继续280rpm强力搅拌2小时，最后通过喷雾干燥得到干燥的氢氧化铒(Er(OH)3)包覆LiNi0.5Co0.2Mn0.3O2的正极复合活性物质(以复合活性物质的重量为基准，添加剂的含量为7.8重量％)。
实施例20
按照实施例1的方法制备锂离子电池A20，不同的是，用氢氧化铌(Nb(OH)5)包覆LiNi0.5Co0.2Mn0.3O2的正极复合活性物质代替氢氧化铝包覆LiNi0.5Co0.2Mn0.3O2的正极复合活性物质，其中，氢氧化铌(Nb(OH)5)包覆LiNi0.5Co0.2Mn0.3O2的正极复合活性物质按如下方法制备：
将929g金属铌溶解于由3200g质量分数为65％的浓硝酸和5000g质量分数为40％的氢氟酸组成的混合溶液中，制得铌液，在搅拌条件下，向铌液中逐步加入质量分数为25％的氨水，直至反应体系pH值为7.3，控制加氨水时间为2小时，反应结束后得到氢氧化铌前驱体。将该前驱体用去离子水洗涤以去除其中的硝酸铵和氟化铵，随后将作为活性成分的21034g化学式为LiNi0.5Co0.2Mn0.3O2的锂镍钴锰氧正极材料加入其中，加入24000g去离子水，380rpm强力搅拌2小时，最后通过喷雾干燥得到干燥的氢氧化铌(Nb(OH)5)包覆LiNi0.5Co0.2Mn0.3O2的正极复合活性物质(以复合活性物质的重量为基准，添加剂的含量为7.8重量％)。
实施例21
按照实施例1的方法制备锂离子电池A21，不同的是，用氢氧化铬(Cr(OH)3)包覆LiNi0.5Co0.2Mn0.3O2的正极复合活性物质代替氢氧化铝包覆LiNi0.5Co0.2Mn0.3O2的正极复合活性物质，其中，氢氧化铬(Cr(OH)3)包覆LiNi0.5Co0.2Mn0.3O2的正极复合活性物质按如下方法制备：
将4000g九水硝酸铬溶解在15000g去离子水中，制得硝酸铬溶液，在搅拌条件下，向硝酸铬溶液中逐步加入质量分数为25％的氨水，直至反应体系pH值为7.3，控制加氨水时间为2小时，反应结束后得到氢氧化铬沉淀。将该沉淀用去离子水洗涤以去除其中的硝酸铵，将作为活性成分的12175g化学式为LiNi0.5Co0.2Mn0.3O2的锂镍钴锰氧正极材料加入其中，加入14000g去离子水，继续250rpm强力搅拌2小时，最后通过喷雾干燥得到干燥的氢氧化铬(Cr(OH)3)包覆LiNi0.5Co0.2Mn0.3O2的正极复合活性物质(以复合活性物质的重量为基准，添加剂的含量为7.8重量％)。
实施例22
按照实施例1的方法制备锂离子电池A22，不同的是，用氢氧化钼(Mo(OH)3)包覆LiNi0.5Co0.2Mn0.3O2的正极复合活性物质代替氢氧化铝包覆LiNi0.5Co0.2Mn0.3O2的正极复合活性物质，其中，氢氧化钼(Mo(OH)3)包覆LiNi0.5Co0.2Mn0.3O2的正极复合活性物质按如下方法制备：
在搅拌条件下，将2560g三水三氯化钼溶解在25000g无水乙醇中，得到澄清溶液，在搅拌条件下，向该澄清溶液中逐步加入2150g质量分数为25％的氨水，控制加氨水时间为2小时，反应结束后得到氢氧化钼沉淀。将该沉淀用去离子水洗涤以去除其中的氯化铵，并用异丙醇置换水，随后将作为活性成分的17369g化学式为LiNi0.5Co0.2Mn0.3O2的锂镍钴锰氧正极材料加入其中，加入20000g异丙醇，继续270rpm强力搅拌2小时，最后通过喷雾干燥得到干燥的氢氧化钼(Mo(OH)3)包覆LiNi0.5Co0.2Mn0.3O2的正极复合活性物质(以复合活性物质的重量为基准，添加剂的含量为7.8重量％)。
实施例23
按照实施例1的方法制备锂离子电池A23，不同的是，用氢氧化亚锰(Mn(OH)2)包覆LiNi0.5Co0.2Mn0.3O2的正极复合活性物质代替氢氧化铝包覆LiNi0.5Co0.2Mn0.3O2的正极复合活性物质，其中，氢氧化亚锰(Mn(OH)2)包覆LiNi0.5Co0.2Mn0.3O2的正极复合活性物质按如下方法制备：
将3580g的50重量％硝酸亚锰水溶液用15000g去离子水稀释，制得硝酸亚锰溶液，在搅拌及氮气保护的条件下，向硝酸亚锰溶液中逐步加入质量分数为25％的氨水，直至反应体系pH值为7.3，控制加氨水时间为2小时，反应结束后得到氢氧化亚锰沉淀。在氮气保护下，将该沉淀用去离子水洗涤以去除其中的硝酸铵，并用异丙醇置换水，随后将作为活性成分的10513g化学式为LiNi0.5Co0.2Mn0.3O2的锂镍钴锰氧正极材料加入其中，加入13000g异丙醇，继续240rpm强力搅拌2小时，最后通过喷雾干燥得到干燥的氢氧化亚锰(Mn(OH)2)包覆LiNi0.5Co0.2Mn0.3O2的正极复合活性物质(以复合活性物质的重量为基准，添加剂的含量为7.8重量％)。
实施例24
按照实施例1的方法制备锂离子电池A24，不同的是，用氢氧化铁(Fe(OH)3)包覆LiNi0.5Co0.2Mn0.3O2的正极复合活性物质代替羟基氢氧化铝包覆LiNi0.5Co0.2Mn0.3O2的正极复合活性物质，其中，氢氧化铁(Fe(OH)3)包覆LiNi0.5Co0.2Mn0.3O2的正极复合活性物质按如下方法制备：
将4040g九水硝酸铁用15000g去离子水溶解，制得硝酸铁溶液，在260rpm强力搅拌的条件下，向硝酸铁溶液中快速加入质量分数为25％的氨水，直至反应体系pH值为11，反应结束后得到沉淀。将该沉淀用去离子水快速洗涤以去除其中的硝酸铵和氨水，并用异丙醇置换水，将作为活性成分的12630g化学式为LiNi0.5Co0.2Mn0.3O2的锂镍钴锰氧正极材料加入其中，加入15000g异丙醇，继续250rpm强力搅拌2小时，通过喷雾干燥得到氢氧化铁(Fe(OH)3)包覆LiNi0.5Co0.2Mn0.3O2的正极复合活性物质(以复合活性物质的重量为基准，添加剂的含量为7.8重量％)。
实施例25
按照实施例1的方法制备锂离子电池A25，不同的是，用氢氧化亚钴(Co(OH)2)包覆LiNi0.5Co0.2Mn0.3O2的正极复合活性物质代替氢氧化铝包覆LiNi0.5Co0.2Mn0.3O2的正极复合活性物质，其中，氢氧化亚钴(Co(OH)2)包覆LiNi0.5Co0.2Mn0.3O2的正极复合活性物质按如下方法制备：
将2910g的六水硝酸亚钴用15000g去离子水溶解，制得硝酸亚钴溶液，在搅拌及氮气保护的条件下，向硝酸亚钴溶液中逐步加入质量分数为25％的氨水，直至反应体系pH值为7.3，控制加氨水时间为2小时，反应结束后得到氢氧化亚钴沉淀。在氮气保护的条件下，将该沉淀用去离子水洗涤以去除其中的硝酸铵，并用异丙醇置换水，随后将作为活性成分的10984g化学式为LiNi0.5Co0.2Mn0.3O2的锂镍钴锰氧正极材料加入其中，加入13000g异丙醇，继续290rpm强力搅拌2小时，最后通过喷雾干燥得到干燥的氢氧化亚钴(Co(OH)2)包覆LiNi0.5Co0.2Mn0.3O2的正极复合活性物质(以复合活性物质的重量为基准，添加剂的含量为7.8重量％)。
实施例26
按照实施例1的方法制备锂离子电池A26，不同的是，用氢氧化亚镍(Ni(OH)2)包覆LiNi0.5Co0.2Mn0.3O2的正极复合活性物质代替氢氧化铝包覆LiNi0.5Co0.2Mn0.3O2的正极复合活性物质，其中，氢氧化亚镍(Ni(OH)2)包覆LiNi0.5Co0.2Mn0.3O2的正极复合活性物质按如下方法制备：
将2910g的六水硝酸亚镍用15000g去离子水溶解，制得硝酸亚镍溶液，在搅拌及氮气保护的条件下，向硝酸亚镍溶液中逐步加入质量分数为25％的氨水，直至反应体系pH值为7.3，控制加氨水时间为2小时，反应结束后得到氢氧化亚镍沉淀。在氮气保护的条件下，将该沉淀用去离子水洗涤以去除其中的硝酸铵，并用异丙醇置换水，随后将 作为活性成分的10956g化学式为LiNi0.5Co0.2Mn0.3O2的锂镍钴锰氧正极材料加入其中，加入13000g异丙醇，继续300rpm强力搅拌2小时，最后通过喷雾干燥得到干燥的氢氧化亚镍(Ni(OH)2)包覆LiNi0.5Co0.2Mn0.3O2的正极复合活性物质(以复合活性物质的重量为基准，添加剂的含量为7.8重量％)。
实施例27
按照实施例1的方法制备锂离子电池A27，不同的是，用氢氧化锡(Sn(OH)4)包覆LiNi0.5Co0.2Mn0.3O2的正极复合活性物质代替氢氧化铝包覆LiNi0.5Co0.2Mn0.3O2的正极复合活性物质，其中，氢氧化锡(Sn(OH)4)包覆LiNi0.5Co0.2Mn0.3O2的正极复合活性物质按如下方法制备：
将3510g五水四氯化锡溶解在20000g无水乙醇中，得到澄清溶液，在搅拌条件下，向该澄清溶液中逐步加入2860g质量分数为25％的氨水，控制加氨水时间为2小时，反应结束后得到氢氧化锡沉淀。将该沉淀用去离子水洗涤以去除其中的氯化铵，并用异丙醇置换水，随后将作为活性成分的22070g化学式为LiNi0.5Co0.2Mn0.3O2的锂镍钴锰氧正极材料加入其中，加入24000g异丙醇，继续320rpm强力搅拌2小时，最后通过喷雾干燥得到干燥的氢氧化锡(Sn(OH)4)包覆LiNi0.5Co0.2Mn0.3O2的正极复合活性物质(以复合活性物质的重量为基准，添加剂的含量为7.8重量％)。
实施例28
按照实施例1的方法制备锂离子电池A28，不同的是，用氢氧化铋(Bi(OH)3)包覆LiNi0.5Co0.2Mn0.3O2的正极复合活性物质代替氢氧化铝包覆LiNi0.5Co0.2Mn0.3O2的正极复合活性物质，其中，氢氧化铋(Bi(OH)3)包覆LiNi0.5Co0.2Mn0.3O2的正极复合活性物质按如下方法制备：
将4850g五水硝酸铋加入质量分数为2％的20000g稀硝酸水溶液中溶解，制得硝酸铋溶液，在330rpm强力搅拌条件下，将硝酸铋溶液快速加入2600g质量分数为25％的氨水中，反应结束后得到氢氧化铋沉淀。将该沉淀用去离子水洗涤以去除其中的硝酸铵和氨水，随后将作为活性成分的30733g化学式为LiNi0.5Co0.2Mn0.3O2的锂镍钴锰氧正极材料加入其中，加入33000g去离子水，继续330rpm强力搅拌2小时，并通过喷雾干燥得到干燥的氢氧化铋(Bi(OH)3)包覆LiNi0.5Co0.2Mn0.3O2的正极复合活性物质(以复合活性物质的重量为基准，添加剂的含量为7.8重量％)。
实施例29
按照实施例1的方法制备锂离子电池A29，不同的是，用氢氧化锑(Sb(OH)3)覆LiNi0.5Co0.2Mn0.3O2的正极复合活性物质代替氢氧化铝包覆LiNi0.5Co0.2Mn0.3O2的正极复合活性物质，其中，氢氧化锑(Sb(OH)3)包覆LiNi0.5Co0.2Mn0.3O2的正极复合活性物质按如下方法制备：
在搅拌条件下，将2280g三氯化锑溶解在25000g无水乙醇中，得到澄清溶液，在搅拌条件下，向该澄清溶液中逐步加入2150g质量分数为25％的氨水，控制加氨水时间为2小时，反应结束后得到氢氧化锑沉淀。将该沉淀用去离子水洗涤以去除其中的氯化铵，并用异丙醇置换水，将作为活性成分的20420g化学式为LiNi0.5Co0.2Mn0.3O2的锂镍钴锰氧正极材料加入其中，加入23000g异丙醇，继续340rpm强力搅拌2小时，最后通过喷雾干燥得到干燥的氢氧化锑(Sb(OH)3)包覆LiNi0.5Co0.2Mn0.3O2的正极复合活性物质(以复合活性物质的重量为基准，添加剂的含量为7.8重量％)。
实施例30
按照实施例1的方法制备锂离子电池A30，不同的是，用硼酸(B(OH)3)包覆LiNi0.5Co0.2Mn0.3O2的正极复合活性物质代替氢氧化铝包覆LiNi0.5Co0.2Mn0.3O2的正极复合活性物质，其中，硼酸(B(OH)3)包覆LiNi0.5Co0.2Mn0.3O2的正极复合活性物质按如下方法制备：
将618g硼酸加入15000g去离子水中溶解，制得硼酸溶液，将作为活性成分的7305g化学式为LiNi0.5Co0.2Mn0.3O2的锂镍钴锰氧正极材料加入其中，加入10000g去离子水，300rpm强力搅拌2小时，将该溶液喷雾干燥得到干燥的硼酸(B(OH)3)包覆LiNi0.5Co0.2Mn0.3O2的正极复合活性物质(以复合活性物质的重量为基准，添加剂的含量为7.8重量％)。
实施例31
按照实施例1的方法制备锂离子电池A31，不同的是，用氢氧化铍(Be(OH)2)包覆LiNi0.5Co0.2Mn0.3O2的正极复合活性物质代替氢氧化铝包覆LiNi0.5Co0.2Mn0.3O2的正极复合活性物质，其中，氢氧化铍(Be(OH)2)包覆LiNi0.5Co0.2Mn0.3O2的正极复合活性物质按如下方法制备：
将1870g三水硝酸铍用10000g去离子水溶解，制得硝酸铍溶液，在搅拌条件下，向硝酸铍溶液中逐步加入质量分数为25％的氨水，直至反应体系pH值为7.3，控制加氨水时间为2小时，反应结束后得到氢氧化铍前驱体。将该前驱体用去离子水洗涤以去除其中的硝酸铵，将作为活性成分的5083g化学式为LiNi0.5Co0.2Mn0.3O2的锂镍钴锰氧正极材料加入其中，加入7000g去离子水，继续340rpm强力搅拌2小时，将该溶液喷雾干燥得到干燥的氢氧化铍(Be(OH)2)包覆LiNi0.5Co0.2Mn0.3O2的正极复合活性物质(以复合活性物质的重量为基准，添加剂的含量为7.8重量％)。
实施例32
按照实施例1的方法制备锂离子电池A32，不同的是，用氢氧化镁(Mg(OH)2)包覆LiNi0.5Co0.2Mn0.3O2的正极复合活性物质代替氢氧化铝包覆LiNi0.5Co0.2Mn0.3O2的正极复合活性物质，其中，氢氧化镁(Mg(OH)2)包覆LiNi0.5Co0.2Mn0.3O2的正极复合活性物质按如下方法制备：
将2560g六水硝酸镁用10000g去离子水溶解，制得硝酸镁溶液，在搅拌条件下，向硝酸镁溶液中逐步加入质量分数为25％的氨水，直至反应体系pH值为7.3，控制加氨水时间为2小时，反应结束后得到氢氧化镁沉淀。将该前驱体用去离子水洗涤以去除其中的硝酸铵，将作为活性成分的6891g化学式为LiNi0.5Co0.2Mn0.3O2的锂镍钴锰氧正极材料加入其中，加入9000g去离子水，继续270rpm强力搅拌2小时，将该溶液喷雾干燥得到干燥的氢氧化镁(Mg(OH)2)包覆LiNi0.5Co0.2Mn0.3O2的正极复合活性物质(以复合活性物质的重量为基准，添加剂的含量为7.8重量％)。
实施例33
按照实施例1的方法制备锂离子电池A33，不同的是，用氢氧化铜(Cu(OH)2)包覆LiNi0.5Co0.2Mn0.3O2的正极复合活性物质代替氢氧化铝包覆LiNi0.5Co0.2Mn0.3O2的正极复合活性物质，其中，氢氧化铜(Cu(OH)2)包覆LiNi0.5Co0.2Mn0.3O2的正极复合活性物质按如下方法制备：
将2420g三水硝酸铜用10000g去离子水溶解，制得硝酸铜溶液，在搅拌条件下，向硝酸铜溶液中逐步加入质量分数为25％的氨水，直至反应体系pH值为7.3，控制加氨水时间为2小时，反应结束后得到氢氧化铜沉淀。将该沉淀用去离子水洗涤以去除其中的硝酸铵，将作为活性成分的11530g化学式为LiNi0.5Co0.2Mn0.3O2的锂镍钴锰氧正极 材料加入其中，加入14000g去离子水，继续290rpm强力搅拌2小时，将该溶液喷雾干燥得到干燥的氢氧化铜(Cu(OH)2)包覆LiNi0.5Co0.2Mn0.3O2的正极复合活性物质(以复合活性物质的重量为基准，添加剂的含量为7.8重量％)。
实施例34
按照实施例1的方法制备锂离子电池A34，不同的是，用氢氧化锌(Zn(OH)2)包覆LiNi0.5Co0.2Mn0.3O2的正极复合活性物质代替氢氧化铝包覆LiNi0.5Co0.2Mn0.3O2的正极复合活性物质，其中，氢氧化锌(Zn(OH)2)包覆LiNi0.5Co0.2Mn0.3O2的正极复合活性物质按如下方法制备：
将2970g六水硝酸锌用10000g去离子水溶解，制得硝酸锌溶液，在搅拌条件下，向硝酸锌溶液中逐步加入质量分数为25％的氨水，直至反应体系pH值为7.3，控制加氨水时间为2小时，反应结束后得到氢氧化锌沉淀。将该沉淀用去离子水洗涤以去除其中的硝酸铵，将作为活性成分的11747g化学式为LiNi0.5Co0.2Mn0.3O2的锂镍钴锰氧正极材料加入其中，加入14000g去离子水，继续360rpm强力搅拌2小时，将该溶液喷雾干燥得到干燥的氢氧化锌(Zn(OH)2)包覆LiNi0.5Co0.2Mn0.3O2的正极复合活性物质(以复合活性物质的重量为基准，添加剂的含量约为7.8重量％)。
对比例1
按照实施例1的方法制备锂离子电池D1，不同的是，(1)LiNi0.5Co0.2Mn0.3O2锂镍钴锰氧正极材料未用添加剂进行表面包覆，电池正极极片制备时采用未进行表面包覆的LiNi0.5Co0.2Mn0.3O2锂镍钴锰氧正极材料；
(2)电池正极极片制备时，正极敷料双面面密度调整为305.5g/m2(电池中正极活性成分锂镍钴锰氧的重量与实施例1相同)。
对比例2
按照实施例2的方法制备锂离子电池D2，不同的是，(1)LiNi0.8Co0.15Al0.05O2锂镍钴铝氧正极材料未用添加剂进行表面包覆，电池正极极片制备时采用未进行表面包覆的LiNi0.8Co0.15Al0.05O2锂镍钴铝氧正极材料；
(2)电池正极极片制备时，正极敷料双面面密度调整为305.5g/m2(电池中正极活性成分锂镍钴铝氧的重量与实施例2相同)。
对比例3
按照实施例3的方法制备锂离子电池D3，不同的是，(1)钴酸锂LiCoO2正极材料未用添加剂进行表面包覆，电池正极极片制备采用未进行表面包覆的钴酸锂LiCoO2正极材料；
(2)电池正极极片制备时，正极敷料双面面密度调整为305.5g/m2(电池中正极活性成分钴酸锂的重量与实施例3相同)。
试验例
单体电池的滥用测试
1、过充测试
将单体电池(包括实施例1-34制得的锂离子电池A1-A34以及对比例1-3制得的锂离子电池D1-D3)以30A的电流充电至8.5V，并在8.5V的电压下恒压保持1小时，观察并记录过程中的现象。各取30只单体电池做平行测试。结果见表1。
2、30％挤压测试
将单体电池(包括实施例1-34制得的锂离子电池A1-A34以及对比例1-3制得的锂离子电池D1-D3)以30A的电流充电至4.25V，并在4.25V的电压下恒压充电直至电流小于1.5A。用两块半径为75mm的半圆柱体的端面从垂直于电池极片方向挤压电池，挤压速度为5mm/s，直至电池变形量达到30％，挤压完成后停留一小时，观察并记录过程中的现象。各取30只单体电池做平行测试。结果见表2。
3、50％挤压测试
将单体电池(包括实施例1-34制得的锂离子电池A1-A34以及对比例1-3制得的锂离子电池D1-D3)以30A的电流充电至4.25V，并在4.25V的电压下恒压充电直至电流小于1.5A。用两块半径为75mm的半圆柱体的端面从垂直于电池极片方向挤压电池，挤压速度为5mm/s，直至电池变形量达到50％，挤压完成后停留一小时，观察并记录过程中的现象。各取30只单体电池做平行测试。结果见表3。
4、针刺测试
将单体电池(包括实施例1-34制得的锂离子电池A1-A34以及对比例1-3制得的锂离子电池D1-D3)以30A的电流充电至4.25V，并在4.25V的电压下恒压充电直至电流小于1.5A。用直径为6毫米的钉子沿垂直于电池长宽面的方向，以25mm/s的速度匀速穿过电池，并停留一小时，观察并记录过程中的现象。各取30只单体电池做平行测试。结果见表4。
表1
Figure PCTCN2016113807-appb-000001
Figure PCTCN2016113807-appb-000002
表2
Figure PCTCN2016113807-appb-000003
Figure PCTCN2016113807-appb-000004
表3
Figure PCTCN2016113807-appb-000005
Figure PCTCN2016113807-appb-000006
表4
Figure PCTCN2016113807-appb-000007
Figure PCTCN2016113807-appb-000008
将表1-4中各实施例和对比例的数据比较可知，在制备正极或负极时引入本发明的锂离子电池复合活性物质，能够明显提高由此制备得到的锂离子电池的安全性。
将表1-4中实施例1与实施例7-9的结果比较可知，在制备正极或负极时引入以锂离子电池复合活性物质的重量为基准，添加剂含量为5.7-9.9重量％的锂离子电池复合活性物质，能够进一步提高由此制备得到的锂离子电池的安全性，而当添加剂用量进一步增加时还能够进一步提高制备得到的锂离子电池在极苛刻条件下的安全性。
将表1-4中实施例1-4与实施例10-34的结果比较可知，所述添加剂为氢氧化铝、原硅酸和氢氧化钛中的至少一种时，能够进一步提高制备得到的锂离子电池的安全性。
以上详细描述了本发明的优选实施方式，但是，本发明并不限于上述实施方式中的具体细节，在本发明的技术构思范围内，可以对本发明的技术方案进行多种简单变型，这些简单变型均属于本发明的保护范围。
另外需要说明的是，在上述具体实施方式中所描述的各个具体技术特征，在不矛盾的情况下，可以通过任何合适的方式进行组合，为了避免不必要的重复，本发明对各种可能的组合方式不再另行说明。
此外，本发明的各种不同的实施方式之间也可以进行任意组合，只要其不违背本发明的思想，其同样应当视为本发明所公开的内容。

Claims (10)

  1. 一种锂离子电池复合活性物质，其特征在于，所述锂离子电池复合活性物质为添加剂包覆的活性物质，所述添加剂为M(OH)a，其中，M为IIA族金属元素、IB族金属元素、IIB族金属元素、IIIB族金属元素、IVB族金属元素、VB族金属元素、VIB族金属元素、VIIB族金属元素、VIII族金属元素、IIIA族金属元素、IVA族金属元素、VA族金属元素、硼和硅中的至少一种元素，a＞0。
  2. 根据权利要求1所述的锂离子电池复合活性物质，其中，所述添加剂中，所述IIA族金属元素为Be和/或Mg，所述IB族金属元素为Cu，所述IIB族金属元素为Zn，所述IIIB族金属元素为Y、Sc、La、Ce、Nd、Sm、Gd和Er中的至少一种，所述IVB族金属元素为Ti和/或Zr，所述VB族金属元素为V和/或Nb，所述VIB族金属元素为Cr和/或Mo，所述VIIB族金属元素为Mn，所述VIII族金属元素为Fe、Co和Ni中的至少一种，所述IIIA族金属元素为Al，所述IVA族金属元素为Sn，所述VA族金属元素为Bi和/或Sb；
    优选地，所述添加剂为氢氧化铝、原硅酸和氢氧化钛中的至少一种。
  3. 根据权利要求1或2所述的锂离子电池复合活性物质，其中，以所述锂离子电池复合活性物质的重量为基准，所述添加剂的含量为0.05-30重量％，优选为2-15.3重量％，进一步优选为5.7-9.9重量％。
  4. 根据权利要求1-3中任意一项所述的锂离子电池复合活性物质，其中，所述活性物质为正极活性物质或负极活性物质，所述正极活性物质为钴酸锂、锂镍氧、锂镍钴氧、锂镍钴铝氧、锂镍钴锰氧、锂镍锰氧、锰酸锂、钒酸锂、磷酸铁锂、磷酸锰锂、磷酸锰铁锂、磷酸锰铁镍锂、磷酸锰铁钴锂、磷酸锰铁镍钴锂、磷酸钒锂和硅酸铁锂中的至少一种，所述负极活性物质为石墨、钛酸锂、硅、硬碳、锡和氧化锡中的至少一种。
  5. 权利要求1-4中任意一项所述的锂离子电池复合活性物质的制备方法，其特征在于，该方法包括：制备元素M的氢氧化物沉淀，在分散剂存在下，将所述元素M的氢氧化物沉淀与活性物质混合，然后将所得混合物进行热处理。
  6. 根据权利要求5所述的方法，其中，所述分散剂为异丙醇、去离子水、乙醇、丁醇和丙酮中的至少一种。
  7. 根据权利要求5所述的方法，其中，所述热处理的方式为喷雾干燥、微波干燥、流化床干燥或烘箱干燥，优选为喷雾干燥。
  8. 一种锂离子电池电极浆料，其特征在于，所述电极浆料包括锂离子电池活性物质、粘结剂、导电剂、溶剂和任选的增稠剂，其中，所述锂离子电池活性物质为权利要求1-4中任意一项所述的锂离子电池复合活性物质；
    优选地，以所述锂离子电池复合活性物质的重量为基准，所述粘结剂以干基计的含量为0.5-5重量％，所述导电剂的含量为0.5-5重量％，所述溶剂的含量为55-200重量％，所述增稠剂的含量为0-2.5重量％。
  9. 一种锂离子电池正极或负极，其特征在于，所述锂离子电池正极或负极包括集流体及位于集流体上的电极敷料，所述电极敷料含有锂离子电池活性物质、粘结剂、导 电剂和任选的增稠剂，其中，所述锂离子电池活性物质为权利要求1-4中任意一项所述的锂离子电池复合活性物质。
  10. 一种锂离子电池，其特征在于，所述锂离子电池包括电池壳体以及位于电池壳体内部的电芯组件和电解液，所述电芯组件包括正极、负极和隔膜，且所述正极为权利要求9所述的锂离子电池正极，和/或所述负极为权利要求9所述的锂离子电池负极。
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