WO2018120387A1 - 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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WO2018120387A1
WO2018120387A1 PCT/CN2017/074515 CN2017074515W WO2018120387A1 WO 2018120387 A1 WO2018120387 A1 WO 2018120387A1 CN 2017074515 W CN2017074515 W CN 2017074515W WO 2018120387 A1 WO2018120387 A1 WO 2018120387A1
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active material
ion battery
lithium
lithium ion
positive electrode
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PCT/CN2017/074515
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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
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • 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
    • H01M4/139—Processes of manufacture
    • H01M4/1397—Processes of manufacture of electrodes based on inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/362—Composites
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/362—Composites
    • H01M4/366—Composites as layered products
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/38—Selection of substances as active materials, active masses, active liquids of elements 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
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • H01M4/5825—Oxygenated metallic salts or polyanionic structures, e.g. borates, phosphates, silicates, olivines
    • 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(PO 4 ) a (HPO) 4 ) b ⁇ cH 2 O, 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 Group VIB metal element, a Group VIIB metal element, a Group VIII metal At least one of the element and the VA group metal element, a ⁇ 0, b ⁇ 0, and a, b are not 0 at the same time, c > 0.
  • the present invention provides a method for preparing a lithium ion battery composite active material, which comprises: preparing a hydrated phosphate of element M, and hydrating a phosphate of the element M with an active material in the presence of a dispersant Mixing and then subjecting the resulting mixture to heat treatment.
  • 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 additive of the present invention must contain crystal water to improve the lithium ion battery
  • the safety performance is presumed to be due to the fact that under the abuse condition, the additive contained in the battery absorbs the heat generated by the battery by absorbing the crystal water by the heat absorption, thereby avoiding the thermal runaway of the battery, thereby improving the safety of the 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(PO 4 ) a (HPO 4 ) b ⁇ cH 2 O, 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 Group VIB metal element, a Group VIIB metal element, a Group VIII metal element, and a Group VA metal At least one of the elements, a ⁇ 0, b ⁇ 0, and a, b are not 0 at the same time, c > 0.
  • the Group IIA metal element is Mg
  • the Group IB metal element is Cu
  • the Group IIB metal element is Zn
  • the Group IIIB metal 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 VIB metal element is Cr
  • the Group VIIB metal is Mn
  • the Group VIII metal element is at least one of Fe, Co, and Ni
  • the VA group metal element is Bi.
  • 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 additive is hydrated orthophosphate chromium (CrPO 4 ⁇ 7/2H 2 O), cobalt octahydrate orthophosphate (normalized formula is Co(PO 4 ) 2/3 ⁇ 8/3H 2 O) and at least one of hydrated magnesium phosphate (normalized formula of Mg(PO 4 ) 0.6 (HPO 4 ) 0.1 ⁇ 3/2H 2 O).
  • the content of the additive is preferably 0.05-32 by weight based on the weight of the lithium ion battery composite active material. % is further preferably from 3 to 15% by weight, still more preferably from 5.6-1.6% by weight.
  • 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 hydrated phosphate of element M, and hydrating a phosphate of the element M with an active material in the presence of a dispersant Mixing and then subjecting the resulting mixture to heat treatment.
  • 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 hydrated phosphate of the above-mentioned 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.
  • drying is carried out at a temperature of not more than 150 ° C or hydrothermal treatment with water as a main solvent at a temperature of not more than 200 ° C, hydrated phosphate of element M
  • the crystal water in the medium is not lost, that is, the hydrated phosphate of the element M still contains crystal water; but the heat treatment at not lower than 400 ° C completely removes the crystal water in the hydrated phosphate of the element M, that is, the obtained element M phosphate does not contain crystal water.
  • the residual impurities in the hydrated phosphate of the prepared element M are removed before the hydrated phosphate of the element M is mixed with the active material.
  • the method of the impurities 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 precipitated hydrated phosphate 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 hydrated phosphate 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 specific temperatures and times, the selection may be made according to different drying methods, which are well known to those skilled in the art and will not be described herein.
  • the mixture obtained by mixing the hydrated phosphate of the element M with the active material is dried at a temperature of not more than 150 ° C, the hydrated phosphate of the element M and The crystal water in the composite active material of the prepared lithium ion battery is not lost, that is, the hydrated phosphate of the element M and the lithium ion battery composite active material prepared therefrom still contain crystal water; but at not lower than 400 ° C
  • the heat treatment completely removes the hydrated phosphate of the element M and the crystal water in the lithium ion battery composite active material prepared therefrom, that is, the obtained element M phosphate and the lithium ion battery composite active material prepared therefrom do not contain Crystal water.
  • 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 amount of the hydrated phosphate precipitate of the element M and the amount of the active material.
  • the content of the lithium ion battery composite active material preferably, the amount of the hydrated phosphate precipitate of the control element M and the active material is such that the content of the additive is 0.05-32% by weight based on the weight of the lithium ion battery composite active material. It is further preferably from 3 to 15% by weight, still more preferably from 5.6-1.6% by weight.
  • 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 from 3 to 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. Alkene, carbon nanotubes, carbon fiber (VGCF), At least one of 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 0.05-22 by weight based on the dry weight of the electrode dressing. % is further preferably from 3 to 15% by weight, more preferably from 5.5 to 10.5% 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 invention.
  • the positive electrode of the lithium ion battery or the negative electrode is the negative electrode of the lithium ion battery according to the present 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 present 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.
  • chromium nitrate nonahydrate 4000 g was dissolved in 20,000 g of deionized water to prepare a chromium nitrate solution, and 1640 g of anhydrous trisodium phosphate was dissolved in 16,000 g of deionized water to obtain a trisodium phosphate solution.
  • the above two solutions were mixed under stirring, and the pH of the mixed system was adjusted to 5 with a concentrated phosphoric acid having a mass fraction of 85%, and the mixing time was controlled for 2 hours to obtain a suspension.
  • the suspension was then transferred to a hydrothermal reaction vessel and heat treated at 180 ° C for 10 hours under stirring to obtain a precipitate.
  • the precipitate was washed with deionized water to remove sodium ions and phosphates, and vacuum filtered to obtain a uniform filter cake L1, 100 g of L1 was taken, and the water was replaced with absolute ethanol, and then under an air atmosphere at 100 ° C. After heat treatment for 5 hours, a dry solid was obtained, and the weight was found to be 28.42 g, whereby the solid content of the filter cake L1 was estimated to be 28.42%.
  • 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 323 g of filter cake L1, 1500 g of deionized water was added, vigorously stirred at 290 rpm for 5 hours, and spray dried at 110 ° C.
  • 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 340.7 g/m 2 (the density of the double-sided surface of the dressing was measured by the weight after drying, the same below, The content of the additive was 7.9% by weight based on the dry weight of the electrode dressing, and then dried at 110 ° C to obtain a positive electrode tab.
  • 12480g natural graphite anode material, 130g thickener CMC, 130g conductive agent Super-P and 520g styrene-butadiene rubber latex binder are mixed by: 12500g deionized water as solvent, and the thickener CMC is dissolved. 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 161.6 g/m 2 (based on the weight after drying, the same below), and then at 100 Drying at ° C 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 lithium nickel cobalt manganese active ingredient is about 191 g
  • the negative electrode active material Natural graphite weighs approximately 104g and the battery has a nominal capacity of 30Ah.
  • 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 in accordance with the method of Example 1, except that the coating of LiNi 0.8 Co was coated with cobalt octahydrate (normalized as Co(PO 4 ) 2/3 ⁇ 8/3H 2 O) additive.
  • a positive electrode composite active material of 0.15 Al 0.05 O 2 is used instead of chromium orthophosphate (CrPO 4 ⁇ 7/2H 2 O) to coat a positive electrode composite active material of LiNi 0.5 Co 0.2 Mn 0.3 O 2 , wherein cobalt octahydrate octahydrate ( A normalized composite active material having a normalized formula of Co(PO 4 ) 2/3 ⁇ 8/3H 2 O) additive coated with LiNi 0.8 Co 0.15 Al 0.05 O 2 was prepared as follows:
  • the precipitate was washed with deionized water to remove sodium ions and phosphates, and vacuum filtered to obtain a uniform filter cake L2, 100 g of L2 was taken, and the water was replaced with absolute ethanol, and then under a nitrogen atmosphere at 100 ° C. After heat treatment for 5 hours, a dry solid was obtained, and the weight was found to be 26.57 g, whereby the solid content of the filter cake L2 was estimated to be 26.57%.
  • a lithium ion battery A3 was prepared according to the method of Example 1, except that the hydrated magnesium phosphate (normalized by the formula Mg(PO 4 ) 0.6 (HPO 4 ) 0.1 ⁇ 3/2H 2 O) was coated with LiCoO 2 .
  • a positive electrode composite active material instead of chromic orthophosphate (CrPO 4 ⁇ 7/2H 2 O) coated with LiNi 0.5 Co 0.2 Mn 0.3 O 2 as a positive electrode composite active material, wherein hydrated magnesium phosphate (normalized formula is Mg) (PO 4 ) 0.6 (HPO 4 ) 0.1 ⁇ 3/2H 2 O)
  • the positive electrode composite active material coated with LiCoO 2 as an additive was prepared as follows:
  • magnesium nitrate hexahydrate 2560g was dissolved in 10000g of deionized water to prepare a magnesium nitrate solution, and 984g of anhydrous trisodium phosphate and 358g of disodium hydrogen phosphate dodecahydrate were dissolved in 10000g of deionized water to obtain trisodium phosphate and hydrogen phosphate.
  • Sodium mixed solution Under stirring, the magnesium nitrate solution was mixed with a mixed solution of trisodium phosphate and disodium hydrogen phosphate, and the mixing time was controlled to 2 hours to obtain a suspension. The suspension was then transferred to a hydrothermal reaction vessel and heat treated at 180 ° C for 10 hours under stirring to obtain a precipitate.
  • the precipitate was washed with deionized water to remove sodium ions and phosphates, and vacuum filtered to obtain a uniform filter cake L3, 100 g of L3 was taken, water was replaced with absolute ethanol, and then air-conditioned at 100 ° C. After heat treatment for 5 hours, a dry solid was obtained, and the weight was found to be 25.82 g, whereby the solid content of the filter cake L3 was estimated to be 25.82%. 1000 g of lithium cobaltate positive electrode material of LiCoO 2 as an active ingredient was added to 355 g of filter cake L3, 1500 g of deionized water was added, vigorously stirred at 350 rpm for 5 hours, and spray dried at 110 ° C to obtain hydrated magnesium phosphate (normalized).
  • the general formula is Mg(PO 4 ) 0.6 (HPO 4 ) 0.1 ⁇ 3/2H 2 O) a positive electrode composite active material coated with LiCoO 2 (the content of the additive is 8.4% by weight based on the weight of the composite active material).
  • a lithium ion battery A4 was prepared in accordance with the method of Example 1, except that:
  • LiNi 0.5 Co 0.2 Mn 0.3 O 2 lithium nickel cobalt manganese oxide cathode material was not surface coated with additives, and the battery positive electrode sheet was prepared by surface coating without LiNi 0.5 Co 0.2 Mn 0.3 O 2 lithium nickel cobalt manganese.
  • Oxygen cathode material, and the double-sided surface density of the dressing is 312.1g/m 2 when the battery positive electrode sheet is prepared;
  • the surface coated hydrated chromium orthophosphate (CrPO 4 ⁇ 7/2H) is used. 2 O)
  • the specific method for preparing natural graphite coated with chrome orthophosphate (CrPO 4 ⁇ 7/2H 2 O) additive is:
  • chromium nitrate nonahydrate 4000 g was dissolved in 20,000 g of deionized water to prepare a chromium nitrate solution, and 1640 g of anhydrous trisodium phosphate was dissolved in 16,000 g of deionized water to obtain a trisodium phosphate solution.
  • the above two solutions were mixed under stirring, and the pH of the mixed system was adjusted to 5 with a concentrated phosphoric acid having a mass fraction of 85%, and the mixing time was controlled for 2 hours to obtain a suspension.
  • the suspension was then transferred to a hydrothermal reaction vessel and heat treated at 180 ° C for 10 hours under stirring to obtain a precipitate.
  • the precipitate was washed with deionized water to remove sodium ions and phosphates, and vacuum filtered to obtain a uniform filter cake L4, 100 g of L4 was taken, and the water was replaced with absolute ethanol, and then at 100 ° C in an air atmosphere. After heat treatment for 5 hours, a dry solid was obtained, and the weight was found to be 28.11 g, whereby the solid content of the filter cake L4 was estimated to be 28.11%.
  • a lithium ion battery A5 was prepared in accordance with the method of Example 1, except that (1) a positive electrode composite active material coated with a surface hydrated chromium orthophosphate (CrPO 4 ⁇ 7/2H 2 O) additive was prepared as follows:
  • chromium nitrate nonahydrate 4000 g was dissolved in 20,000 g of deionized water to prepare a chromium nitrate solution, and 1640 g of anhydrous trisodium phosphate was dissolved in 16,000 g of deionized water to obtain a trisodium phosphate solution.
  • the above two solutions were mixed under stirring, and the pH of the mixed system was adjusted to 5 with a concentrated phosphoric acid having a mass fraction of 85%, and the mixing time was controlled for 2 hours to obtain a suspension.
  • the suspension was then transferred to a hydrothermal reaction vessel and heat treated at 180 ° C for 10 hours under stirring to obtain a precipitate.
  • the precipitate was washed with deionized water to remove sodium ions and phosphates, and vacuum filtered to obtain a uniform filter cake L5, 100 g of L5 was taken, and the water was replaced with absolute ethanol, and then under an air atmosphere, 100 ° C. After heat treatment for 5 hours, a dry solid was obtained, and the weight was found to be 27.85 g, whereby the solid content of the filter cake L5 was estimated to be 27.85%.
  • 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 221 g of filter cake L5, 1500 g of deionized water was added, vigorously stirred at 290 rpm for 5 hours, and spray dried at 105 ° C.
  • a lithium ion battery A6 was prepared in accordance with the method of Example 1, except that (1) a positive electrode composite active material coated with a surface hydrated chromium orthophosphate (CrPO 4 ⁇ 7/2H 2 O) additive was prepared as follows:
  • chromium nitrate nonahydrate 4000 g was dissolved in 20,000 g of deionized water to prepare a chromium nitrate solution, and 1640 g of anhydrous trisodium phosphate was dissolved in 16,000 g of deionized water to obtain a trisodium phosphate solution.
  • the above two solutions were mixed under stirring, and the pH of the mixed system was adjusted to 5 with a concentrated phosphoric acid having a mass fraction of 85%, and the mixing time was controlled for 2 hours to obtain a suspension.
  • the suspension was then transferred to a hydrothermal reaction vessel and heat treated at 180 ° C for 10 hours under stirring to obtain a precipitate.
  • the precipitate was washed with deionized water to remove sodium ions and phosphates, and vacuum filtered to obtain a uniform filter cake L6, 100 g of L6, and water was replaced with absolute ethanol, and then at 100 ° C in an air atmosphere. After heat treatment for 5 hours, a dry solid was obtained, and the weight was found to be 27.38 g, whereby the solid content of the filter cake L6 was 27.38%.
  • 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 428 g of filter cake L6, 1500 g of deionized water was added, vigorously stirred at 290 rpm for 5 hours, and spray dried at 120 ° C.
  • the double-sided surface density of the positive electrode dressing was adjusted to 348.7 g/m 2 (the weight of the positive electrode lithium nickel cobalt manganese oxide active component in the battery was the same as in Example 1).
  • 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 a surface hydrated chromium orthophosphate (CrPO 4 ⁇ 7/2H 2 O) additive was prepared as follows:
  • chromium nitrate nonahydrate 4000 g was dissolved in 20,000 g of deionized water to prepare a chromium nitrate solution, and 1640 g of anhydrous trisodium phosphate was dissolved in 16,000 g of deionized water to obtain a trisodium phosphate solution.
  • the above two solutions were mixed under stirring, and the pH of the mixed system was adjusted to 5 with a concentrated phosphoric acid having a mass fraction of 85%, and the mixing time was controlled for 2 hours to obtain a suspension.
  • the suspension was then transferred to a hydrothermal reaction vessel and heat treated at 180 ° C for 10 hours under stirring to obtain a precipitate.
  • the precipitate was washed with deionized water to remove sodium ions and phosphates, and vacuum filtered to obtain a uniform filter cake L7, 100 g of L7 was taken, and the water was replaced with absolute ethanol, and then at 100 ° C in an air atmosphere. After heat treatment for 5 hours, a dry solid was obtained, and the weight was found to be 29.14 g, whereby the solid content of the filter cake L7 was estimated to be 29.14%.
  • 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 121 g of filter cake L7, 1500 g of deionized water was added, vigorously stirred at 290 rpm for 5 hours, and spray dried at 115 ° C.
  • 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 a surface hydrated chromium orthophosphate (CrPO 4 ⁇ 7/2H 2 O) additive was prepared as follows:
  • chromium nitrate nonahydrate 4000 g was dissolved in 20,000 g of deionized water to prepare a chromium nitrate solution, and 1640 g of anhydrous trisodium phosphate was dissolved in 16,000 g of deionized water to obtain a trisodium phosphate solution.
  • the above two solutions were mixed under stirring, and the pH of the mixed system was adjusted to 5 with a concentrated phosphoric acid having a mass fraction of 85%, and the mixing time was controlled for 2 hours to obtain a suspension.
  • the suspension was then transferred to a hydrothermal reaction vessel and heat treated at 180 ° C for 10 hours under stirring to obtain a precipitate.
  • the precipitate was washed with deionized water to remove sodium ions and phosphates, and vacuum filtered to obtain a uniform filter cake L8, 100 g of L8 was taken, and the water was replaced with absolute ethanol, and then at 100 ° C in an air atmosphere. After heat treatment for 5 hours, a dry solid was obtained, and the weight was found to be 29.14 g, whereby the solid content of the filter cake L8 was estimated to be 29.14%.
  • a lithium ion battery A9 was prepared in accordance with the method of Example 1, except that (1) a positive electrode composite active material coated with a surface hydrated chromium orthophosphate (CrPO 4 ⁇ 7/2H 2 O) additive was prepared as follows:
  • chromium nitrate nonahydrate 4000 g was dissolved in 20,000 g of deionized water to prepare a chromium nitrate solution, and 1640 g of anhydrous trisodium phosphate was dissolved in 16,000 g of deionized water to obtain a trisodium phosphate solution.
  • the above two solutions were mixed under stirring, and the pH of the mixed system was adjusted to 5 with a concentrated phosphoric acid having a mass fraction of 85%, and the mixing time was controlled for 2 hours to obtain a suspension. Then, the suspension was transferred to a hydrothermal reaction vessel, and heat-treated at 180 ° C for 10 hours under stirring to obtain a precipitate.
  • the precipitate was washed with deionized water to remove sodium ions and phosphates, and vacuum filtered to obtain a uniform filter cake L9, 100 g of L9 was taken, water was replaced with absolute ethanol, and then, under an air atmosphere, 100 ° C After heat treatment for 5 hours, a dry solid was obtained, and the weight was 28.60 g, whereby the solid content of the filter cake L9 was estimated to be 28.60%.
  • 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 603 g of filter cake L9, 1500 g of deionized water was added, vigorously stirred at 290 rpm for 5 hours, and spray dried at 110 ° C.
  • 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 titanium monohydrogen phosphate (Ti(HPO 4 ) 2 .2H 2 O). Instead of hydrated chromium orthophosphate (CrPO 4 ⁇ 7/2H 2 O), a positive electrode composite active material coated with LiNi 0.5 Co 0.2 Mn 0.3 O 2 , wherein titanium tetrahydrogen phosphate dihydrate (Ti(HPO 4 ) 2 ⁇ 2H 2 O The positive electrode composite active material coated with LiNi 0.5 Co 0.2 Mn 0.3 O 2 was prepared as follows:
  • the dried solid was obtained and found to have a weight of 25.18 g, thereby estimating the solid content of the filter cake L10 to be 25.18%.
  • 1000 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 364 g of filter cake L10, 1500 g of deionized water was added, vigorously stirred at 370 rpm for 5 hours, and spray dried at 110 ° C.
  • a lithium ion battery A11 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 hydrogen phosphate monohydrate (Zr(HPO 4 ) 2 ⁇ H 2 O). Instead of hydrated chromium orthophosphate (CrPO 4 ⁇ 7/2H 2 O), a positive electrode composite active material coated with LiNi 0.5 Co 0.2 Mn 0.3 O 2 , wherein zirconium hydrogen phosphate monohydrate (Zr(HPO 4 ) 2 ⁇ H 2 O The positive electrode composite active material coated with LiNi 0.5 Co 0.2 Mn 0.3 O 2 was prepared as follows:
  • the precipitate was washed with deionized water to remove chloride ions therein, and vacuum filtered to obtain a uniform filter cake L11, 100 g of L11 was taken, water was replaced with absolute ethanol, and then heat-treated at 100 ° C for 5 hours in an air atmosphere.
  • the dried solid was obtained and found to have a weight of 25.85 g, whereby the solid content of the filter cake L11 was estimated to be 25.85%.
  • 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 355 g of filter cake L11, 1500 g of deionized water was added, vigorously stirred at 330 rpm for 5 hours, and spray dried at 110 ° C.
  • a positive electrode composite active material of LiNi 0.5 Co 0.2 Mn 0.3 O 2 coated with zirconium hydrogen phosphate monohydrate (Zr(HPO 4 ) 2 ⁇ H 2 O) is obtained (based on the weight of the composite active material, the content of the additive is 8.4 weight) %).
  • 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 yttrium orthophosphate monohydrate (YPO 4 ⁇ H 2 O) instead of hydrated orthophosphate chromium. (CrPO 4 ⁇ 7/2H 2 O) a positive electrode composite active material coated with LiNi 0.5 Co 0.2 Mn 0.3 O 2 , wherein YPO 4 ⁇ H 2 O monohydrate is coated with LiNi 0.5 Co 0.2 Mn 0.3 O
  • the positive electrode composite active material of 2 was prepared as follows:
  • the precipitate was washed with deionized water to remove sodium ions and phosphates, and vacuum filtered to obtain a uniform filter cake L12, 100 g of L12 was taken, and the water was replaced with absolute ethanol, and then at 100 ° C in an air atmosphere. After heat treatment for 5 hours, a dry solid was obtained, and the weight was found to be 29.27 g, whereby the solid content of the filter cake L12 was estimated to be 29.27%.
  • 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 313 g of filter cake L12, 1500 g of deionized water was added, vigorously stirred at 300 rpm for 5 hours, and spray dried at 110 ° C.
  • a positive electrode composite active material of LiNi 0.5 Co 0.2 Mn 0.3 O 2 coated with yttrium orthophosphate monohydrate (YPO 4 ⁇ H 2 O) was obtained (the content of the additive was 8.4% by weight based on the weight of the composite active material).
  • a lithium ion battery A13 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 strontium orthophosphate monohydrate (ScPO 4 ⁇ H 2 O) instead of hydrated chromium orthophosphate. (CrPO 4 ⁇ 7/2H 2 O) a positive electrode composite active material coated with LiNi 0.5 Co 0.2 Mn 0.3 O 2 , wherein strontium orthophosphate monohydrate (ScPO 4 ⁇ H 2 O) is coated with LiNi 0.5 Co 0.2 Mn 0.3 O
  • the positive electrode composite active material of 2 was prepared as follows:
  • the precipitate was washed with deionized water to remove sodium ions and phosphates, and vacuum filtered to obtain a uniform filter cake L13, 100 g of L13 was taken, and the water was replaced with absolute ethanol, and then at 100 ° C in an air atmosphere. After heat treatment for 5 hours, a dry solid was obtained, and the weight was found to be 29.49 g, whereby the solid content of the filter cake L13 was estimated to be 29.49%.
  • 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 311 g of filter cake L13, 1500 g of deionized water was added, vigorously stirred at 300 rpm for 5 hours, and spray dried at 110 ° C.
  • a lithium ion battery A14 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 orthophosphate monohydrate (LaPO 4 ⁇ H 2 O) instead of hydrated chromium orthophosphate. (CrPO 4 ⁇ 7/2H 2 O) a positive electrode composite active material coated with LiNi 0.5 Co 0.2 Mn 0.3 O 2 , wherein lanthanum orthophosphate monohydrate (LaPO 4 ⁇ H 2 O) is coated with LiNi 0.5 Co 0.2 Mn 0.3 O
  • the positive electrode composite active material of 2 was prepared as follows:
  • the precipitate was washed with deionized water to remove sodium ions and phosphates, and vacuum filtered to obtain a uniform filter cake L14, 100 g of L14 was taken, and the water was replaced with absolute ethanol, and then at 100 ° C in an air atmosphere. After heat treatment for 5 hours, a dry solid was obtained, and the weight was found to be 30.66 g, whereby the solid content of the filter cake L14 was estimated to be 30.66%.
  • 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 299 g of filter cake L14, 1500 g of deionized water was added, vigorously stirred at 260 rpm for 5 hours, and spray dried at 110 ° C.
  • a positive electrode composite active material of LaNi 0.5 Co 0.2 Mn 0.3 O 2 coated with lanthanum orthophosphate monohydrate (LaPO 4 ⁇ H 2 O) was obtained (the content of the additive was 8.4% by weight based on the weight of the composite active material).
  • 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 lanthanum orthophosphate monohydrate (CePO 4 ⁇ H 2 O) instead of hydrated chromium orthophosphate. (CrPO 4 ⁇ 7/2H 2 O) a positive electrode composite active material coated with LiNi 0.5 Co 0.2 Mn 0.3 O 2 , wherein cerium orthophosphate monohydrate (CePO 4 ⁇ H 2 O) is coated with LiNi 0.5 Co 0.2 Mn 0.3 O
  • the positive electrode composite active material of 2 was prepared as follows:
  • the precipitate was washed with deionized water to remove sodium ions and phosphates, and vacuum filtered to obtain a uniform filter cake L15, 100 g of L15 was taken, and the water was replaced with absolute ethanol, and then at 100 ° C in an air atmosphere.
  • the heat treatment was carried out for 5 hours to obtain a dried solid, and the weight was found to be 30.03 g, whereby the solid content of the filter cake L15 was estimated to be 30.03%.
  • 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 305 g of filter cake L15, 1500 g of deionized water was added, vigorously stirred at 280 rpm for 5 hours, and spray dried at 110 ° C.
  • a positive electrode composite active material of LiNi 0.5 Co 0.2 Mn 0.3 O 2 coated with lanthanum orthophosphate monohydrate (CePO 4 ⁇ H 2 O) was obtained (the content of the additive was 8.4% by weight based on the weight of the composite active material).
  • a lithium ion battery A16 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 ruthenium orthophosphate monohydrate (NdPO 4 ⁇ H 2 O) instead of hydrated chromium orthophosphate. (CrPO 4 ⁇ 7/2H 2 O) a positive electrode composite active material coated with LiNi 0.5 Co 0.2 Mn 0.3 O 2 , wherein NdPO 4 ⁇ H 2 O monohydrate is coated with LiNi 0.5 Co 0.2 Mn 0.3 O
  • the positive electrode composite active material of 2 was prepared as follows:
  • the precipitate was washed with deionized water to remove sodium ions and phosphates, and vacuum filtered to obtain a uniform filter cake L16, 100 g of L16 was taken, and the water was replaced with absolute ethanol, and then under an air atmosphere at 100 ° C. After heat treatment for 5 hours, a dry solid was obtained, and the weight was 27.62 g, and the solid content of the filter cake L16 was estimated to be 27.62%.
  • 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 strontium orthophosphate monohydrate (SmPO 4 ⁇ H 2 O) instead of hydrated chromium orthophosphate. (CrPO 4 ⁇ 7/2H 2 O) a positive electrode composite active material coated with LiNi 0.5 Co 0.2 Mn 0.3 O 2 , wherein bismuth orthophosphate monohydrate (SmPO 4 ⁇ H 2 O) is coated with LiNi 0.5 Co 0.2 Mn 0.3 O
  • the positive electrode composite active material of 2 was prepared as follows:
  • the precipitate was washed with deionized water to remove sodium ions and phosphates, and vacuum filtered to obtain a uniform filter cake L17, 100 g of L17 was taken, and the water was replaced with absolute ethanol, and then under an air atmosphere, 100 ° C. After heat treatment for 5 hours, a dry solid was obtained, and the weight was found to be 27.26 g, whereby the solid content of the filter cake L17 was estimated to be 27.26%.
  • 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 336 g of filter cake L17, 1500 g of deionized water was added, vigorously stirred at 240 rpm for 5 hours, and spray dried at 110 ° C.
  • a lithium ion battery A18 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 yttrium orthophosphate monohydrate (GdPO 4 ⁇ H 2 O) instead of hydrated orthophosphate chromium. (CrPO 4 ⁇ 7/2H 2 O) a positive electrode composite active material coated with LiNi 0.5 Co 0.2 Mn 0.3 O 2 , wherein ruthenium orthophosphate monohydrate (GdPO 4 ⁇ H 2 O) is coated with LiNi 0.5 Co 0.2 Mn 0.3 O
  • the positive electrode composite active material of 2 was prepared as follows:
  • the precipitate was washed with deionized water to remove sodium ions and phosphates, and vacuum filtered to obtain a uniform filter cake L18, 100 g of L18 was taken, and the water was replaced with absolute ethanol, and then in an air atmosphere at 100 ° C. After heat treatment for 5 hours, a dry solid was obtained, and the weight was found to be 29.32 g, whereby the solid content of the filter cake L18 was estimated to be 29.32%.
  • 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 ruthenium orthophosphate monohydrate (ErPO 4 ⁇ H 2 O) instead of hydrated chromium orthophosphate. (CrPO 4 ⁇ 7/2H 2 O) a positive electrode composite active material coated with LiNi 0.5 Co 0.2 Mn 0.3 O 2 , wherein erbium orthophosphate monohydrate (ErPO 4 ⁇ H 2 O) is coated with LiNi 0.5 Co 0.2 Mn 0.3 O
  • the positive electrode composite active material of 2 was prepared as follows:
  • cerium nitrate pentahydrate 4433 g was dissolved in 20,000 g of deionized water to prepare a cerium nitrate solution, and 1640 g of anhydrous trisodium phosphate was dissolved in 16,000 g of deionized water to obtain a trisodium phosphate solution.
  • the above two solutions were mixed under stirring, and the pH of the mixed system was adjusted to 5 with a concentrated phosphoric acid having a mass fraction of 85%, and the mixing time was controlled for 2 hours to obtain a suspension.
  • the suspension was then transferred to a hydrothermal reaction vessel and heat treated at 180 ° C for 10 hours under stirring to obtain a precipitate.
  • the precipitate was washed with deionized water to remove sodium ions and phosphates, and vacuum filtered to obtain a uniform filter cake L19, 100 g of L19 was taken, and the water was replaced with absolute ethanol, and then at 100 ° C in an air atmosphere. After heat treatment for 5 hours, a dry solid was obtained, and the weight was 28.73 g, whereby the solid content of the filter cake L19 was estimated to be 28.73%.
  • a lithium ion battery A20 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 iron orthophosphate dihydrate (FePO 4 ⁇ 2H 2 O) was used instead of hydrated chromium orthophosphate. (CrPO 4 ⁇ 7/2H 2 O) a positive electrode composite active material coated with LiNi 0.5 Co 0.2 Mn 0.3 O 2 , wherein iron orthophosphate dihydrate (FePO 4 ⁇ 2H 2 O) is coated with LiNi 0.5 Co 0.2 Mn 0.3 O
  • the positive electrode composite active material of 2 was prepared as follows:
  • the precipitate was washed with deionized water to remove sodium ions and phosphates, and vacuum filtered to obtain a uniform filter cake L20, 100 g of L20 was taken, and the water was replaced with absolute ethanol, and then at 100 ° C in an air atmosphere. After heat treatment for 5 hours, a dry solid was obtained, and the weight was found to be 26.05 g, whereby the solid content of the filter cake L20 was estimated to be 26.05%.
  • 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 352 g of filter cake L20, 1500 g of deionized water was added, and the mixture was vigorously stirred at 270 rpm for 5 hours, and spray dried at 110 ° C.
  • a lithium ion battery A21 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 orthophosphate monohydrate (MnPO 4 ⁇ H 2 O) instead of chromic orthophosphate. (CrPO 4 ⁇ 7/2H 2 O) a positive electrode composite active material coated with LiNi 0.5 Co 0.2 Mn 0.3 O 2 , wherein manganese orthophosphate monohydrate (MnPO 4 ⁇ H 2 O) is coated with LiNi 0.5 Co 0.2 Mn 0.3 O
  • the positive electrode composite active material of 2 was prepared as follows:
  • 3580 g of a 50 wt% aqueous solution of manganese nitrate was diluted with 20,000 g of deionized water to prepare a manganese nitrate solution, and 1640 g of anhydrous trisodium phosphate was dissolved in 16,000 g of deionized water to obtain a trisodium phosphate solution.
  • the above two solutions were mixed under stirring, and the pH of the mixed system was adjusted to 3 with concentrated nitric acid having a mass fraction of 65%, and the mixing time was controlled for 2 hours to obtain a suspension.
  • the suspension was then transferred to a hydrothermal reaction vessel and heat treated at 180 ° C for 10 hours under stirring to obtain a precipitate.
  • the precipitate was washed with deionized water to remove sodium ions and phosphates, and vacuum filtered to obtain a uniform filter cake L21, 100 g of L21 was taken, and the water was replaced with absolute ethanol, and then in an air atmosphere at 100 ° C.
  • the heat treatment was carried out for 5 hours to obtain a dried solid, and the weight was found to be 27.16 g, whereby the solid content of the filter cake L21 was 27.16%.
  • a lithium ion battery A22 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 nickel orthophosphate monohydrate (NiPO 4 ⁇ H 2 O) was used instead of hydrated orthophosphate chromium. (CrPO 4 ⁇ 7/2H 2 O) a positive electrode composite active material coated with LiNi 0.5 Co 0.2 Mn 0.3 O 2 , wherein nickel nicotinate monohydrate (NiPO 4 ⁇ H 2 O) is coated with LiNi 0.5 Co 0.2 Mn 0.3 O
  • the positive electrode composite active material of 2 was prepared as follows:
  • 2910 g of nickel hexahydrate hexahydrate was dissolved in 20,000 g of deionized water to prepare a nickel nitrate solution, and 1640 g of anhydrous trisodium phosphate was dissolved in 16,000 g of deionized water to obtain a trisodium phosphate solution.
  • the above two solutions were mixed under stirring, and the pH of the mixed system was adjusted to 3 with concentrated nitric acid having a mass fraction of 65%, and the mixing time was controlled for 2 hours to obtain a suspension.
  • the suspension was then transferred to a hydrothermal reaction vessel and heat treated at 180 ° C for 10 hours under stirring to obtain a precipitate.
  • the precipitate was washed with deionized water to remove sodium ions and phosphates, and vacuum filtered to obtain a uniform filter cake L22, 100 g of L22 was taken, and the water was replaced with absolute ethanol, and then at 100 ° C in an air atmosphere. After heat treatment for 5 hours, a dry solid was obtained, and the weight was found to be 26.64 g, whereby the solid content of the filter cake L22 was estimated to be 26.64%.
  • 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 344 g of filter cake L22, 1500 g of deionized water was added, vigorously stirred at 240 rpm for 5 hours, and spray dried at 110 ° C.
  • a lithium ion battery A23 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 coated with bismuth orthophosphate (BiPO 4 ⁇ 2/3H 2 O) was used instead of hydrated orthophosphoric acid.
  • Chromium (CrPO 4 ⁇ 7/2H 2 O) coated with a positive electrode composite active material of LiNi 0.5 Co 0.2 Mn 0.3 O 2 , wherein hydrated orthophosphoric acid ruthenium (BiPO 4 ⁇ 2/3H 2 O) is coated with LiNi 0.5 Co 0.2 Mn 0.3 O 2 positive active material composite was prepared as follows:
  • the precipitate was washed with deionized water to remove sodium ions and phosphates, and vacuum filtered to obtain a uniform filter cake L23, 100 g of L23 was taken, and the water was replaced with absolute ethanol, and then at 100 ° C in an air atmosphere. After heat treatment for 5 hours, a dry solid was obtained, and the weight was found to be 30.44 g, whereby the solid content of the filter cake L23 was estimated to be 30.44%.
  • 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 301 g of filter cake L23, 1500 g of deionized water was added, vigorously stirred at 220 rpm for 5 hours, and spray dried at 110 ° C.
  • a lithium ion battery A24 was prepared according to the method of Example 1, except that copper phosphate trihydrate (normalized to Cu(PO 4 ) 2 /3 ⁇ H 2 O) was coated with LiNi 0.5 Co 0.2 Mn 0.3 O a positive electrode composite active material of 2 , which is substituted with chromic orthophosphate (CrPO 4 ⁇ 7/2H 2 O), and a positive electrode composite active material coated with LiNi 0.5 Co 0.2 Mn 0.3 O 2 , wherein copper phosphate trihydrate (normalized formula is Cu(PO 4 ) 2/3 ⁇ H 2 O)
  • a positive electrode composite active material coated with LiNi 0.5 Co 0.2 Mn 0.3 O 2 was prepared as follows:
  • the precipitate was washed with deionized water to remove sodium ions and phosphates, and vacuum filtered to obtain a uniform filter cake L24, 100 g of L24 was taken, and the water was replaced with absolute ethanol, and then at 100 ° C in an air atmosphere. After heat treatment for 5 hours, a dry solid was obtained, and the weight was found to be 28.80 g, whereby the solid content of the filter cake L24 was estimated to be 28.80%.
  • a lithium ion battery A25 was prepared according to the method of Example 1, except that zinc phosphate dihydrate (normalized to Zn(PO 4 ) 2/3 ⁇ 2/3H 2 O) was coated with LiNi 0.5 Co 0.2 Mn.
  • a positive electrode composite active material of the formula Zn(PO 4 ) 2/3 ⁇ 2/3H 2 O) coated with LiNi 0.5 Co 0.2 Mn 0.3 O 2 was prepared as follows:
  • the precipitate was washed with deionized water to remove sodium ions and phosphates, and vacuum filtered to obtain a uniform filter cake L25, 100 g of L25 was taken, and the water was replaced with absolute ethanol, and then at 100 ° C in an air atmosphere.
  • the heat treatment was carried out for 5 hours to obtain a dried solid, and the weight was found to be 29.26 g, whereby the solid content of the filter cake L25 was estimated to be 29.26%.
  • 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;
  • a lithium ion battery D4 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 chromium orthophosphate (CrPO 4 , containing no crystal water) was used instead of chromium orthophosphate ( CrPO 4 ⁇ 7/2H 2 O) a positive electrode composite active material coated with LiNi 0.5 Co 0.2 Mn 0.3 O 2 , wherein chromium orthophosphate (CrPO 4 , free of crystal water) is coated with LiNi 0.5 Co 0.2 Mn 0.3 O 2
  • the positive electrode composite active material was prepared as follows:
  • chromium nitrate nonahydrate 4000 g was dissolved in 20,000 g of deionized water to prepare a chromium nitrate solution, and 1640 g of anhydrous trisodium phosphate was dissolved in 16,000 g of deionized water to obtain a trisodium phosphate solution.
  • the above two solutions were mixed under stirring, and the pH of the mixed system was adjusted to 5 with a concentrated phosphoric acid having a mass fraction of 85%, and the mixing time was controlled for 2 hours to obtain a suspension.
  • the suspension was then transferred to a hydrothermal reaction vessel and heat treated at 180 ° C for 10 hours under stirring to obtain a precipitate.
  • the precipitate was washed with deionized water to remove sodium ions and phosphates, and vacuum filtered to obtain a uniform filter cake L26, 100 g of L26, and water was replaced with absolute ethanol, and then in an air atmosphere at 500 ° C. After heat treatment for 8 hours, a dry solid was obtained, and the weight was found to be 25.88 g, whereby the content of chromium orthophosphate (CrPO 4 , containing no crystal water) in the filter cake L26 was estimated to be 25.88%.
  • CrPO 4 chromium orthophosphate
  • a lithium ion battery D5 was prepared according to the method of Example 2 except that Cobalt Orthophosphate (normalized to Co(PO 4 ) 2/3 , free of water of crystallization) was coated with LiNi 0.8 Co 0.15 Al 0.05.
  • O composite positive electrode active material in place of 2 cobaltous orthophosphate octahydrate (normalized formula Co (PO 4) 2/3 ⁇ 8 / 3H 2 O) coated with LiNi 0.8 Co 0.15 Al 0.05 O 2 composite positive electrode active
  • the substance, wherein the cobalt orthophosphate (normalized formula is Co(PO 4 ) 2/3 , free of crystal water) and the positive electrode composite active material coated with LiNi 0.8 Co 0.15 Al 0.05 O 2 is prepared as follows:
  • the precipitate was washed with deionized water to remove sodium ions and phosphates, and vacuum filtered to obtain a uniform filter cake L27, 100 g of L27 was taken, and the water was replaced with absolute ethanol, and then under a nitrogen atmosphere at 500 ° C. After heat treatment for 8 hours, a dry solid was obtained, and the weight was 19.57 g, thereby estimating the content of cobalt orthophosphate (normalized formula of Co(PO 4 ) 2/3 , containing no crystal water) in the filter cake L27. 19.57%.
  • a lithium ion battery D6 was prepared according to the method of Example 3 except that magnesium cobaltate (normalized to Mg(PO 4 ) 0.6 (HPO 4 ) 0.1 , free of crystal water) was coated with lithium cobalt oxide LiCoO 2 .
  • a positive electrode composite active material instead of hydrated magnesium phosphate (normalized to Mg(PO 4 ) 0.6 (HPO 4 ) 0.1 ⁇ 3/2H 2 O) coated with LiCoO 2 positive electrode composite active material, wherein magnesium phosphate
  • a positive electrode composite active material having a general formula of Mg(PO 4 ) 0.6 (HPO 4 ) 0.1 and containing no crystal water) coated with lithium cobaltate LiCoO 2 was prepared as follows:
  • magnesium nitrate hexahydrate 2560g was dissolved in 10000g of deionized water to prepare a magnesium nitrate solution, and 984g of anhydrous trisodium phosphate and 358g of disodium hydrogen phosphate dodecahydrate were dissolved in 10000g of deionized water to obtain trisodium phosphate and hydrogen phosphate.
  • Sodium mixed solution Under stirring, the magnesium nitrate solution was mixed with a mixed solution of trisodium phosphate and disodium hydrogen phosphate, and the mixing time was controlled to 2 hours to obtain a suspension. The suspension was then transferred to a hydrothermal reaction vessel and heat treated at 180 ° C for 10 hours under stirring to obtain a precipitate.
  • the precipitate was washed with deionized water to remove sodium ions and phosphates, and vacuum filtered to obtain a uniform filter cake L28, 100 g of L28, and water was replaced with absolute ethanol, and then at 500 ° C in an air atmosphere. After heat treatment for 5 hours, a dry solid was obtained, and the weight was 19.24 g, thereby estimating the magnesium phosphate in the filter cake L28 (normalized formula of Mg(PO 4 ) 0.6 (HPO 4 ) 0.1 , containing no crystal water) The content is 19.24%.
  • the single cells (including the lithium ion batteries A1-A25 prepared in Examples 1-25 and the lithium ion batteries D1-D6 prepared in Comparative Examples 1-6) 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-A25 prepared in Examples 1-25 and the lithium ion batteries D1-D6 prepared in Comparative Examples 1-6) 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-A25 prepared in Examples 1-25 and the lithium ion batteries D1-D6 prepared in Comparative Examples 1-6) 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-A25 prepared in Examples 1-25 and the lithium ion batteries D1-D6 prepared in Comparative Examples 1-6) 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.
  • the lithium ion battery composite active material obtained by coating the active material with the hydrated phosphate additive according to the present invention when preparing the positive electrode or the negative electrode can be significantly improved.
  • the safety of the lithium ion battery thus prepared, and the introduced additive must contain crystal water, and when the corresponding substance containing no crystal water is introduced, the corresponding substance cannot effectively absorb the heat of the battery under the abuse condition, and thus cannot be obtained.
  • Example 1 Comparing the results of Example 1 and Examples 7-9 in Tables 1-4, it is known that lithium ions having an additive content of 5.6-10.6% by weight 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.
  • the additive is hydrated chromium orthophosphate (CrPO 4 ⁇ 7/2H 2 O), cobalt octahydrate orthophosphate (normalized)
  • the general formula is Co(PO 4 ) 2/3 ⁇ 8/3H 2 O) and hydrated magnesium phosphate (normalized formula is Mg(PO 4 ) 0.6 (HPO 4 ) 0.1 ⁇ 3/2H 2 O) At least one of them can further improve the safety of the prepared lithium ion battery.

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Abstract

本发明涉及锂离子电池技术领域，公开了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。该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(PO4)a(HPO4)b·cH2O，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、VIB族金属元素、VIIB族金属元素、VIII族金属元素和VA族金属元素中的至少一种元素，a≥0，b≥0，且a，b不同时为0，c>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(PO4)a(HPO4)b·cH2O，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、VIB族金属元素、VIIB族金属元素、VIII族金属元素和VA族金属元素中的至少一种元素，a≥0，b≥0，且a，b不同时为0，c>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的水合磷酸盐，在分散剂存在下，将所述元素M的水合磷酸盐与活性物质混合，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无不良影响。其中，本发明的添加剂中必须含有结晶水时才能提高锂离子电池 的安全性能，推测其原因可能是，在滥用条件下，电池中所含添加剂通过吸热分解放出结晶水的方式吸收电池产生的热量，避免了电池的热失控，从而提升了电池的安全性。
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(PO4)a(HPO4)b·cH2O，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、VIB族金属元素、VIIB族金属元素、VIII族金属元素和VA族金属元素中的至少一种元素，a≥0，b≥0，且a，b不同时为0，c>0。
其中，本领域技术人员应该理解的是，M(PO4)a(HPO4)b·cH2O中，a和b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VIB族金属元素为Cr，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VA族金属元素为Bi。
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，所述添加剂为水合正磷酸铬(CrPO4·7/2H2O)、八水合正磷酸亚钴(归一化通式为Co(PO4)2/3·8/3H2O)和水合磷酸镁(归一化通式为Mg(PO4)0.6(HPO4)0.1·3/2H2O)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0.05-32重量％，进一步优选为3-15重量％，更进一步优选为5.6-10.6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的水合磷酸盐，在分散剂存在下，将所述元素M的水合磷酸盐与活性物质混合，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的水合磷酸盐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。其中，本领域技术人员应该理解的是，在制备过程中，在不大于150℃的温度下进行干燥或者在不大于200℃的温度下以水作为主要溶剂进行水热处理，元素M的水合磷酸盐中的结晶水不会丢失，即元素M的水合磷酸盐中仍含结晶水；但在不低于400℃下进行热处理，会彻底除去元素M的水合磷酸盐中的结晶水，即得到的元素M的磷酸盐中不含结晶水。
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的水合磷酸盐与活性物质混合之前，先将制备得到的元素M的水合磷酸盐中残留的杂质除去，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的水合磷酸盐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的水合磷酸盐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，可以根据不同的干燥方式进行选择，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，将元素M的水合磷酸盐与活性物质混合所得的混合物在不大于150℃的温度下进行干燥，元素M的水合磷酸盐和由其制备的锂离子电池复合活性物质中的结晶水不会丢失，即元素M的水合磷酸盐和由其制备的锂离子电池复合活性物质中仍均含结晶水；但在不低于400℃下进行热处理，会彻底除去元素M的水合磷酸盐和由其制备的锂离子电池复合活性物质中的结晶水，即得到的元素M的磷酸盐和由其制备的锂离子电池复合活性物质中均不含结晶水。
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的水合磷酸盐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的水合磷酸盐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0.05-32重量％，进一步优选为3-15重量％，更进一步优选为5.6-10.6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0.05-22重量％，进一步优选为3-15重量％，更优选为5.5-10.5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.表面包覆水合正磷酸铬添加剂的复合活性物质的制备
将4000g九水硝酸铬用20000g去离子水溶解，制得硝酸铬溶液，将1640g无水磷酸三钠用16000g去离子水溶解，得到磷酸三钠溶液。在搅拌的条件下，将上述两种溶液混合，并用质量分数为85％的浓磷酸调节混合体系pH值为5，控制混合时间为2小时，得到悬浮液。然后将该悬浮液转移至水热反应釜，在搅拌的条件下，180℃热处理10小时，得到沉淀。将该沉淀用去离子水洗涤以去除其中的钠离子和磷酸根，真空抽滤后得到均匀的滤饼L1，取100g L1，用无水乙醇置换其中的水，然后在空气气氛下，100℃热处理5小时，得到干燥的固体，测得其重量为28.42g，由此推算滤饼L1固含量为28.42％。将作为活性成分的1000g化学式为LiNi0.5Co0.2Mn0.3O2的锂镍钴锰氧正极材料加入323g滤饼L1中，加入1500g去离子水，290rpm下强力搅拌5小时，110℃下喷雾干燥，得到水合正磷酸铬(CrPO4·7/2H2O)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8.4重量％)。
b.单体电池的制作
(1)电池正极极片制备
将23375g上述制备得到的正极复合活性物质、750g粘结剂HSV900、875g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340.7g/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 为7.9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12480g天然石墨负极材料、130g增稠剂CMC、130g导电剂Super-P和520g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161.6g/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，锂镍钴锰氧活性成分的重量约为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，用八水合磷酸亚钴(归一化通式为Co(PO4)2/3·8/3H2O)添加剂包覆LiNi0.8Co0.15Al0.05O2的正极复合活性物质代替用水合正磷酸铬(CrPO4·7/2H2O)包覆LiNi0.5Co0.2Mn0.3O2的正极复合活性物质，其中，八水合磷酸亚钴(归一化通式为Co(PO4)2/3·8/3H2O)添加剂包覆LiNi0.8Co0.15Al0.05O2的正极复合活性物质按如下方法制备：
将2910g六水硝酸亚钴用15000g去离子水溶解，制得硝酸亚钴溶液，将1093g无水磷酸三钠用10000g去离子水溶解，得到磷酸三钠溶液。在搅拌及氮气保护的条件下，将上述两种溶液混合，控制混合时间为2小时，得到悬浮液。然后将该悬浮液转移至水热反应釜，在搅拌及氮气保护的条件下，180℃热处理10小时，得到沉淀。将该沉淀用去离子水洗涤以去除其中的钠离子和磷酸根，真空抽滤后得到均匀的滤饼L2，取100g L2，用无水乙醇置换其中的水，然后在氮气气氛下，100℃热处理5小时，得到干燥的固体，测得其重量为26.57g，由此推算滤饼L2固含量为26.57％。将作为活性成分的1000g化学式为LiNi0.8Co0.15Al0.05O2的锂镍钴铝氧正极材料加入345g滤饼L2中，加入1500g去离子水，氮气气氛下，320rpm下强力搅拌5小时，120℃下喷雾干燥，得到八水合磷酸亚钴(归一化通式为Co(PO4)2/3·8/3H2O)包覆LiNi0.8Co0.15Al0.05O2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8.4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，用水合磷酸镁(归一化通式为Mg(PO4)0.6(HPO4)0.1·3/2H2O)添加剂包覆LiCoO2的正极复合活性物质代替用水合正磷酸铬(CrPO4·7/2H2O)包覆LiNi0.5Co0.2Mn0.3O2的正极复合活性物质，其中，水合磷酸镁(归一化通式为Mg(PO4)0.6(HPO4)0.1·3/2H2O)添加剂包覆LiCoO2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，将984g无水磷酸三钠、358g十二水合磷酸氢二钠用10000g去离子水溶解，得到磷酸三钠、磷酸氢二钠混合溶液。在搅拌的条件下，将硝酸镁溶液与磷酸三钠、磷酸氢二钠混合溶液混合，控制混合时间为2小时，得到悬浮液。然后将该悬浮液转移至水热反应釜，在搅拌的条件下，180℃热处理10小时，得到沉淀。将该沉淀用去离子水洗涤以去除其中的钠离子和磷酸根，真空抽滤后得到均匀的滤饼L3，取100g L3，用无水乙醇置换其中的水，然后在空气气氛下，100℃热处理5小时，得到干燥的固体，测得其重量为25.82g，由此推算滤饼L3固含量为25.82％。将作为活性成分的1000g化学式为LiCoO2的钴酸锂正 极材料加入355g滤饼L3中，加入1500g去离子水，350rpm下强力搅拌5小时，110℃下喷雾干燥，得到水合磷酸镁(归一化通式为Mg(PO4)0.6(HPO4)0.1·3/2H2O)包覆LiCoO2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8.4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312.1g/m2；(2)电池负极极片制备时，采用表面包覆水合正磷酸铬(CrPO4·7/2H2O)添加剂的天然石墨替代未进行表面包覆的天然石墨，制备表面包覆水合正磷酸铬(CrPO4·7/2H2O)添加剂的天然石墨的具体方法为：
将4000g九水硝酸铬用20000g去离子水溶解，制得硝酸铬溶液，将1640g无水磷酸三钠用16000g去离子水溶解，得到磷酸三钠溶液。在搅拌的条件下，将上述两种溶液混合，并用质量分数为85％的浓磷酸调节混合体系pH值为5，控制混合时间为2小时，得到悬浮液。然后将该悬浮液转移至水热反应釜，在搅拌的条件下，180℃热处理10小时，得到沉淀。将该沉淀用去离子水洗涤以去除其中的钠离子和磷酸根，真空抽滤后得到均匀的滤饼L4，取100g L4，用无水乙醇置换其中的水，然后在空气气氛下，100℃热处理5小时，得到干燥的固体，测得其重量为28.11g，由此推算滤饼L4固含量为28.11％。将作为活性成分的1000g天然石墨负极材料加入326g滤饼L4中，加入1500g去离子水，290rpm下强力搅拌5小时，115℃下喷雾干燥，得到水合正磷酸铬(CrPO4·7/2H2O)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8.4重量％)。
(3)负极敷料双面面密度调整为176.4g/m2。
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)表面包覆水合正磷酸铬(CrPO4·7/2H2O)添加剂的正极复合活性物质按如下方法制备：
将4000g九水硝酸铬用20000g去离子水溶解，制得硝酸铬溶液，将1640g无水磷酸三钠用16000g去离子水溶解，得到磷酸三钠溶液。在搅拌的条件下，将上述两种溶液混合，并用质量分数为85％的浓磷酸调节混合体系pH值为5，控制混合时间为2小时，得到悬浮液。然后将该悬浮液转移至水热反应釜，在搅拌的条件下，180℃热处理10小时，得到沉淀。将该沉淀用去离子水洗涤以去除其中的钠离子和磷酸根，真空抽滤后得到均匀的滤饼L5，取100g L5，用无水乙醇置换其中的水，然后在空气气氛下，100℃热处理5小时，得到干燥的固体，测得其重量为27.85g，由此推算滤饼L5固含量为27.85％。将作为活性成分的1000g化学式为LiNi0.5Co0.2Mn0.3O2的锂镍钴锰氧正极材料加入221g滤饼L5中，加入1500g去离子水，290rpm下强力搅拌5小时，105℃下喷雾干燥，得到水合正磷酸铬(CrPO4·7/2H2O)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5.8重量％)。
(2)电池正极极片制备时，正极敷料双面面密度调整为331.3g/m2(电池中正极锂镍钴锰氧活性成分的重量与实施例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)表面包覆水合正磷酸铬(CrPO4·7/2H2O)添加剂的正极复合活性物质按如下方法制备：
将4000g九水硝酸铬用20000g去离子水溶解，制得硝酸铬溶液，将1640g无水磷酸三钠用16000g去离子水溶解，得到磷酸三钠溶液。在搅拌的条件下，将上述两种溶液混合，并用质量分数为85％的浓磷酸调节混合体系pH值为5，控制混合时间为2小时，得到悬浮液。然后将该悬浮液转移至水热反应釜，在搅拌的条件下，180℃热处理10小时，得到沉淀。将该沉淀用去离子水洗涤以去除其中的钠离子和磷酸根，真空抽滤后得到均匀的滤饼L6，取100g L6，用无水乙醇置换其中的水，然 后在空气气氛下，100℃热处理5小时，得到干燥的固体，测得其重量为27.38g，由此推算滤饼L6固含量为27.38％。将作为活性成分的1000g化学式为LiNi0.5Co0.2Mn0.3O2的锂镍钴锰氧正极材料加入428g滤饼L6中，加入1500g去离子水，290rpm下强力搅拌5小时，120℃下喷雾干燥，得到水合正磷酸铬(CrPO4·7/2H2O)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10.5重量％)。
(2)电池正极极片制备时，正极敷料双面面密度调整为348.7g/m2(电池中正极锂镍钴锰氧活性成分的重量与实施例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)表面包覆水合正磷酸铬(CrPO4·7/2H2O)添加剂的正极复合活性物质按如下方法制备：
将4000g九水硝酸铬用20000g去离子水溶解，制得硝酸铬溶液，将1640g无水磷酸三钠用16000g去离子水溶解，得到磷酸三钠溶液。在搅拌的条件下，将上述两种溶液混合，并用质量分数为85％的浓磷酸调节混合体系pH值为5，控制混合时间为2小时，得到悬浮液。然后将该悬浮液转移至水热反应釜，在搅拌的条件下，180℃热处理10小时，得到沉淀。将该沉淀用去离子水洗涤以去除其中的钠离子和磷酸根，真空抽滤后得到均匀的滤饼L7，取100g L7，用无水乙醇置换其中的水，然后在空气气氛下，100℃热处理5小时，得到干燥的固体，测得其重量为29.14g，由此推算滤饼L7固含量为29.14％。将作为活性成分的1000g化学式为LiNi0.5Co0.2Mn0.3O2的锂镍钴锰氧正极材料加入121g滤饼L7中，加入1500g去离子水，290rpm下强力搅拌5小时，115℃下喷雾干燥，得到水合正磷酸铬(CrPO4·7/2H2O)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3.4重量％)。
(2)电池正极极片制备时，正极敷料双面面密度调整为323.1g/m2(电池中正极锂镍钴锰氧活性成分的重量与实施例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)表面包覆水合正磷酸铬(CrPO4·7/2H2O)添加剂的正极复合活性物质按如下方法制备：
将4000g九水硝酸铬用20000g去离子水溶解，制得硝酸铬溶液，将1640g无水磷酸三钠用16000g去离子水溶解，得到磷酸三钠溶液。在搅拌的条件下，将上述两种溶液混合，并用质量分数为85％的浓磷酸调节混合体系pH值为5，控制混合时间为2小时，得到悬浮液。然后将该悬浮液转移至水热反应釜，在搅拌的条件下，180℃热处理10小时，得到沉淀。将该沉淀用去离子水洗涤以去除其中的钠离子和磷酸根，真空抽滤后得到均匀的滤饼L8，取100g L8，用无水乙醇置换其中的水，然后在空气气氛下，100℃热处理5小时，得到干燥的固体，测得其重量为29.14g，由此推算滤饼L8固含量为29.14％。将作为活性成分的1000g化学式为LiNi0.5Co0.2Mn0.3O2的锂镍钴锰氧正极材料加入31g滤饼L8中，加入1500g去离子水，290rpm下强力搅拌5小时，110℃下喷雾干燥，得到水合正磷酸铬(CrPO4·7/2H2O)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314.9g/m2(电池中正极锂镍钴锰氧活性成分的重量与实施例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)表面包覆水合正磷酸铬(CrPO4·7/2H2O)添加剂的正极复合活性物质按如下方法制备：
将4000g九水硝酸铬用20000g去离子水溶解，制得硝酸铬溶液，将1640g无水磷酸三钠用16000g去离子水溶解，得到磷酸三钠溶液。在搅拌的条件下，将上述两种溶液混合，并用质量分数为85％的浓磷酸调节混合体系pH值为5，控制混合时间为2小时，得到悬浮液。然后将该悬浮液转移至水 热反应釜，在搅拌的条件下，180℃热处理10小时，得到沉淀。将该沉淀用去离子水洗涤以去除其中的钠离子和磷酸根，真空抽滤后得到均匀的滤饼L9，取100g L9，用无水乙醇置换其中的水，然后在空气气氛下，100℃热处理5小时，得到干燥的固体，测得其重量为28.60g，由此推算滤饼L9固含量为28.60％。将作为活性成分的1000g化学式为LiNi0.5Co0.2Mn0.3O2的锂镍钴锰氧正极材料加入603g滤饼L9中，加入1500g去离子水，290rpm下强力搅拌5小时，110℃下喷雾干燥，得到水合正磷酸铬(CrPO4·7/2H2O)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14.7重量％)。
(2)电池正极极片制备时，正极敷料双面面密度调整为365.9g/m2(电池中正极锂镍钴锰氧活性成分的重量与实施例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，用二水合磷酸一氢钛(Ti(HPO4)2·2H2O)包覆LiNi0.5Co0.2Mn0.3O2的正极复合活性物质代替水合正磷酸铬(CrPO4·7/2H2O)包覆LiNi0.5Co0.2Mn0.3O2的正极复合活性物质，其中，二水合磷酸一氢钛(Ti(HPO4)2·2H2O)包覆LiNi0.5Co0.2Mn0.3O2的正极复合活性物质按如下方法制备：
在0℃水浴、且300rpm强力搅拌的条件下，将1900g四氯化钛液体缓慢加入2306g质量分数为85％的浓磷酸中，控制加四氯化钛时间为2小时，反应结束后得到悬浮液。然后将该悬浮液转移至水热反应釜，在搅拌的条件下，180℃热处理10小时，得到沉淀。将该沉淀用去离子水洗涤以去除其中的氯离子，真空抽滤后得到均匀的滤饼L10，取100g L10，用无水乙醇置换其中的水，然后在空气气氛下，100℃热处理5小时，得到干燥的固体，测得其重量为25.18g，由此推算滤饼L10固含量为25.18％。将作为活性成分的1000g化学式为LiNi0.5Co0.2Mn0.3O2的锂镍钴锰氧正极材料加入364g滤饼L10中，加入1500g去离子水，370rpm下强力搅拌5小时，110℃下喷雾干燥，得到二水合磷酸一氢钛(Ti(HPO4)2·2H2O)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8.4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，用一水合磷酸一氢锆(Zr(HPO4)2·H2O)包覆LiNi0.5Co0.2Mn0.3O2的正极复合活性物质代替水合正磷酸铬(CrPO4·7/2H2O)包覆LiNi0.5Co0.2Mn0.3O2的正极复合活性物质，其中，一水合磷酸一氢锆(Zr(HPO4)2·H2O)包覆LiNi0.5Co0.2Mn0.3O2的正极复合活性物质按如下方法制备：
在0℃水浴、且280rpm强力搅拌的条件下，将2330g四氯化锆粉末缓慢加入2306g质量分数为85％的浓磷酸中，控制加四氯化锆时间为2小时，反应结束后得到悬浮液。然后将该悬浮液转移至水热反应釜，在搅拌的条件下，180℃热处理10小时，得到沉淀。将该沉淀用去离子水洗涤以去除其中的氯离子，真空抽滤后得到均匀的滤饼L11，取100g L11，用无水乙醇置换其中的水，然后在空气气氛下，100℃热处理5小时，得到干燥的固体，测得其重量为25.85g，由此推算滤饼L11固含量为25.85％。将作为活性成分的1000g化学式为LiNi0.5Co0.2Mn0.3O2的锂镍钴锰氧正极材料加入355g滤饼L11中，加入1500g去离子水，330rpm下强力搅拌5小时，110℃下喷雾干燥，得到一水合磷酸一氢锆(Zr(HPO4)2·H2O)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8.4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，用一水合正磷酸钇(YPO4·H2O)包覆LiNi0.5Co0.2Mn0.3O2的正极复合活性物质代替水合正磷酸铬(CrPO4·7/2H2O)包覆LiNi0.5Co0.2Mn0.3O2的正极复合活性物质，其中，一水合正磷酸钇(YPO4·H2O)包覆LiNi0.5Co0.2Mn0.3O2的正极复合活性物质按如下方法制备：
将3830g六水硝酸钇用10000g去离子水溶解，制得硝酸钇溶液，将1640g无水磷酸三钠用16000g 去离子水溶解，得到磷酸三钠溶液。在搅拌的条件下，将上述两种溶液混合，并用质量分数为85％的浓磷酸调节混合体系pH值为5，控制混合时间为2小时，得到悬浮液。然后将该悬浮液转移至水热反应釜，在搅拌的条件下，180℃热处理10小时，得到沉淀。将该沉淀用去离子水洗涤以去除其中的钠离子和磷酸根，真空抽滤后得到均匀的滤饼L12，取100g L12，用无水乙醇置换其中的水，然后在空气气氛下，100℃热处理5小时，得到干燥的固体，测得其重量为29.27g，由此推算滤饼L12固含量为29.27％。将作为活性成分的1000g化学式为LiNi0.5Co0.2Mn0.3O2的锂镍钴锰氧正极材料加入313g滤饼L12中，加入1500g去离子水，300rpm下强力搅拌5小时，110℃下喷雾干燥，得到一水合正磷酸钇(YPO4·H2O)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8.4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，用一水合正磷酸钪(ScPO4·H2O)包覆LiNi0.5Co0.2Mn0.3O2的正极复合活性物质代替水合正磷酸铬(CrPO4·7/2H2O)包覆LiNi0.5Co0.2Mn0.3O2的正极复合活性物质，其中，一水合正磷酸钪(ScPO4·H2O)包覆LiNi0.5Co0.2Mn0.3O2的正极复合活性物质按如下方法制备：
将3390g六水硝酸钪用10000g去离子水溶解，制得硝酸钪溶液，将1640g无水磷酸三钠用16000g去离子水溶解，得到磷酸三钠溶液。在搅拌的条件下，将上述两种溶液混合，并用质量分数为85％的浓磷酸调节混合体系pH值为5，控制混合时间为2小时，得到悬浮液。然后将该悬浮液转移至水热反应釜，在搅拌的条件下，180℃热处理10小时，得到沉淀。将该沉淀用去离子水洗涤以去除其中的钠离子和磷酸根，真空抽滤后得到均匀的滤饼L13，取100g L13，用无水乙醇置换其中的水，然后在空气气氛下，100℃热处理5小时，得到干燥的固体，测得其重量为29.49g，由此推算滤饼L13固含量为29.49％。将作为活性成分的1000g化学式为LiNi0.5Co0.2Mn0.3O2的锂镍钴锰氧正极材料加入311g滤饼L13中，加入1500g去离子水，300rpm下强力搅拌5小时，110℃下喷雾干燥，得到一水合正磷酸钪(ScPO4·H2O)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8.4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，用一水合正磷酸镧(LaPO4·H2O)包覆LiNi0.5Co0.2Mn0.3O2的正极复合活性物质代替水合正磷酸铬(CrPO4·7/2H2O)包覆LiNi0.5Co0.2Mn0.3O2的正极复合活性物质，其中，一水合正磷酸镧(LaPO4·H2O)包覆LiNi0.5Co0.2Mn0.3O2的正极复合活性物质按如下方法制备：
将4330g六水硝酸镧用20000g去离子水溶解，制得硝酸镧溶液，将1640g无水磷酸三钠用16000g去离子水溶解，得到磷酸三钠溶液。在搅拌的条件下，将上述两种溶液混合，并用质量分数为85％的浓磷酸调节混合体系pH值为5，控制混合时间为2小时，得到悬浮液。然后将该悬浮液转移至水热反应釜，在搅拌的条件下，180℃热处理10小时，得到沉淀。将该沉淀用去离子水洗涤以去除其中的钠离子和磷酸根，真空抽滤后得到均匀的滤饼L14，取100g L14，用无水乙醇置换其中的水，然后在空气气氛下，100℃热处理5小时，得到干燥的固体，测得其重量为30.66g，由此推算滤饼L14固含量为30.66％。将作为活性成分的1000g化学式为LiNi0.5Co0.2Mn0.3O2的锂镍钴锰氧正极材料加入299g滤饼L14中，加入1500g去离子水，260rpm下强力搅拌5小时，110℃下喷雾干燥，得到一水合正磷酸镧(LaPO4·H2O)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8.4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，用一水合正磷酸铈(CePO4·H2O)包覆LiNi0.5Co0.2Mn0.3O2的正极复合活性物质代替水合正磷酸铬(CrPO4·7/2H2O)包覆LiNi0.5Co0.2Mn0.3O2的正极复合活性物质，其中，一水合正磷酸铈(CePO4·H2O)包覆LiNi0.5Co0.2Mn0.3O2的正极复合活性 物质按如下方法制备：
将4340g六水硝酸铈用20000g去离子水溶解，制得硝酸铈溶液，将1640g无水磷酸三钠用16000g去离子水溶解，得到磷酸三钠溶液。在搅拌的条件下，将上述两种溶液混合，并用质量分数为85％的浓磷酸调节混合体系pH值为5，控制混合时间为2小时，得到悬浮液。然后将该悬浮液转移至水热反应釜，在搅拌的条件下，180℃热处理10小时，得到沉淀。将该沉淀用去离子水洗涤以去除其中的钠离子和磷酸根，真空抽滤后得到均匀的滤饼L15，取100g L15，用无水乙醇置换其中的水，然后在空气气氛下，100℃热处理5小时，得到干燥的固体，测得其重量为30.03g，由此推算滤饼L15固含量为30.03％。将作为活性成分的1000g化学式为LiNi0.5Co0.2Mn0.3O2的锂镍钴锰氧正极材料加入305g滤饼L15中，加入1500g去离子水，280rpm下强力搅拌5小时，110℃下喷雾干燥，得到一水合正磷酸铈(CePO4·H2O)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8.4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，用一水合正磷酸钕(NdPO4·H2O)包覆LiNi0.5Co0.2Mn0.3O2的正极复合活性物质代替水合正磷酸铬(CrPO4·7/2H2O)包覆LiNi0.5Co0.2Mn0.3O2的正极复合活性物质，其中，一水合正磷酸钕(NdPO4·H2O)包覆LiNi0.5Co0.2Mn0.3O2的正极复合活性物质按如下方法制备：
将4380g六水硝酸钕用20000g去离子水溶解，制得硝酸钕溶液，将1640g无水磷酸三钠用16000g去离子水溶解，得到磷酸三钠溶液。在搅拌的条件下，将上述两种溶液混合，并用质量分数为85％的浓磷酸调节混合体系pH值为5，控制混合时间为2小时，得到悬浮液。然后将该悬浮液转移至水热反应釜，在搅拌的条件下，180℃热处理10小时，得到沉淀。将该沉淀用去离子水洗涤以去除其中的钠离子和磷酸根，真空抽滤后得到均匀的滤饼L16，取100g L16，用无水乙醇置换其中的水，然后在空气气氛下，100℃热处理5小时，得到干燥的固体，测得其重量为27.62g，由此推算滤饼L16固含量为27.62％。将作为活性成分的1000g化学式为LiNi0.5Co0.2Mn0.3O2的锂镍钴锰氧正极材料加入332g滤饼L16中，加入1500g去离子水，230rpm下强力搅拌5小时，110℃下喷雾干燥，得到一水合正磷酸钕(NdPO4·H2O)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8.4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，用一水合正磷酸钐(SmPO4·H2O)包覆LiNi0.5Co0.2Mn0.3O2的正极复合活性物质代替水合正磷酸铬(CrPO4·7/2H2O)包覆LiNi0.5Co0.2Mn0.3O2的正极复合活性物质，其中，一水合正磷酸钐(SmPO4·H2O)包覆LiNi0.5Co0.2Mn0.3O2的正极复合活性物质按如下方法制备：
将4440g六水硝酸钐用20000g去离子水溶解，制得硝酸钐溶液，将1640g无水磷酸三钠用16000g去离子水溶解，得到磷酸三钠溶液。在搅拌的条件下，将上述两种溶液混合，并用质量分数为85％的浓磷酸调节混合体系pH值为5，控制混合时间为2小时，得到悬浮液。然后将该悬浮液转移至水热反应釜，在搅拌的条件下，180℃热处理10小时，得到沉淀。将该沉淀用去离子水洗涤以去除其中的钠离子和磷酸根，真空抽滤后得到均匀的滤饼L17，取100g L17，用无水乙醇置换其中的水，然后在空气气氛下，100℃热处理5小时，得到干燥的固体，测得其重量为27.26g，由此推算滤饼L17固含量为27.26％。将作为活性成分的1000g化学式为LiNi0.5Co0.2Mn0.3O2的锂镍钴锰氧正极材料加入336g滤饼L17中，加入1500g去离子水，240rpm下强力搅拌5小时，110℃下喷雾干燥，得到一水合正磷酸钐(SmPO4·H2O)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8.4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，用一水合正磷酸钆(GdPO4·H2O)包覆 LiNi0.5Co0.2Mn0.3O2的正极复合活性物质代替水合正磷酸铬(CrPO4·7/2H2O)包覆LiNi0.5Co0.2Mn0.3O2的正极复合活性物质，其中，一水合正磷酸钆(GdPO4·H2O)包覆LiNi0.5Co0.2Mn0.3O2的正极复合活性物质按如下方法制备：
将4510g六水硝酸钆用20000g去离子水溶解，制得硝酸钆溶液，将1640g无水磷酸三钠用16000g去离子水溶解，得到磷酸三钠溶液。在搅拌的条件下，将上述两种溶液混合，并用质量分数为85％的浓磷酸调节混合体系pH值为5，控制混合时间为2小时，得到悬浮液。然后将该悬浮液转移至水热反应釜，在搅拌的条件下，180℃热处理10小时，得到沉淀。将该沉淀用去离子水洗涤以去除其中的钠离子和磷酸根，真空抽滤后得到均匀的滤饼L18，取100g L18，用无水乙醇置换其中的水，然后在空气气氛下，100℃热处理5小时，得到干燥的固体，测得其重量为29.32g，由此推算滤饼L18固含量为29.32％。将作为活性成分的1000g化学式为LiNi0.5Co0.2Mn0.3O2的锂镍钴锰氧正极材料加入313g滤饼L18中，加入1500g去离子水，310rpm下强力搅拌5小时，110℃下喷雾干燥，得到一水合正磷酸钆(GdPO4·H2O)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8.4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，用一水合正磷酸铒(ErPO4·H2O)包覆LiNi0.5Co0.2Mn0.3O2的正极复合活性物质代替水合正磷酸铬(CrPO4·7/2H2O)包覆LiNi0.5Co0.2Mn0.3O2的正极复合活性物质，其中，一水合正磷酸铒(ErPO4·H2O)包覆LiNi0.5Co0.2Mn0.3O2的正极复合活性物质按如下方法制备：
将4433g五水硝酸铒用20000g去离子水溶解，制得硝酸铒溶液，将1640g无水磷酸三钠用16000g去离子水溶解，得到磷酸三钠溶液。在搅拌的条件下，将上述两种溶液混合，并用质量分数为85％的浓磷酸调节混合体系pH值为5，控制混合时间为2小时，得到悬浮液。然后将该悬浮液转移至水热反应釜，在搅拌的条件下，180℃热处理10小时，得到沉淀。将该沉淀用去离子水洗涤以去除其中的钠离子和磷酸根，真空抽滤后得到均匀的滤饼L19，取100g L19，用无水乙醇置换其中的水，然后在空气气氛下，100℃热处理5小时，得到干燥的固体，测得其重量为28.73g，由此推算滤饼L19固含量为28.73％。将作为活性成分的1000g化学式为LiNi0.5Co0.2Mn0.3O2的锂镍钴锰氧正极材料加入319g滤饼L19中，加入1500g去离子水，300rpm下强力搅拌5小时，110℃下喷雾干燥，得到一水合正磷酸铒(ErPO4·H2O)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8.4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，用二水合正磷酸铁(FePO4·2H2O)包覆LiNi0.5Co0.2Mn0.3O2的正极复合活性物质代替水合正磷酸铬(CrPO4·7/2H2O)包覆LiNi0.5Co0.2Mn0.3O2的正极复合活性物质，其中，二水合正磷酸铁(FePO4·2H2O)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，将1640g无水磷酸三钠用16000g去离子水溶解，得到磷酸三钠溶液。在搅拌的条件下，将上述两种溶液混合，并用质量分数为85％的浓磷酸保持混合体系pH值为3，控制混合时间为2小时，得到悬浮液。然后将该悬浮液转移至水热反应釜，在搅拌的条件下，180℃热处理10小时，得到沉淀。将该沉淀用去离子水洗涤以去除其中的钠离子和磷酸根，真空抽滤后得到均匀的滤饼L20，取100g L20，用无水乙醇置换其中的水，然后在空气气氛下，100℃热处理5小时，得到干燥的固体，测得其重量为26.05g，由此推算滤饼L20固含量为26.05％。将作为活性成分的1000g化学式为LiNi0.5Co0.2Mn0.3O2的锂镍钴锰氧正极材料加入352g滤饼L20中，加入1500g去离子水，270rpm下强力搅拌5小时，110℃下喷雾干燥，得到二水合正磷酸铁(FePO4·2H2O)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8.4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，用一水合正磷酸锰(MnPO4·H2O)包覆LiNi0.5Co0.2Mn0.3O2的正极复合活性物质代替水合正磷酸铬(CrPO4·7/2H2O)包覆LiNi0.5Co0.2Mn0.3O2的正极复合活性物质，其中，一水合正磷酸锰(MnPO4·H2O)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20000g去离子水稀释，制得硝酸亚锰溶液，将1640g无水磷酸三钠用16000g去离子水溶解，得到磷酸三钠溶液。在搅拌的条件下，将上述两种溶液混合，并用质量分数为65％的浓硝酸调节混合体系pH值为3，控制混合时间为2小时，得到悬浮液。然后将该悬浮液转移至水热反应釜，在搅拌的条件下，180℃热处理10小时，得到沉淀。将该沉淀用去离子水洗涤以去除其中的钠离子和磷酸根，真空抽滤后得到均匀的滤饼L21，取100g L21，用无水乙醇置换其中的水，然后在空气气氛下，100℃热处理5小时，得到干燥的固体，测得其重量为27.16g，由此推算滤饼L21固含量为27.16％。将作为活性成分的1000g化学式为LiNi0.5Co0.2Mn0.3O2的锂镍钴锰氧正极材料加入338g滤饼L21中，加入1500g去离子水，260rpm下强力搅拌5小时，110℃下喷雾干燥，得到一水合正磷酸锰(MnPO4·H2O)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8.4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，用一水合正磷酸镍(NiPO4·H2O)包覆LiNi0.5Co0.2Mn0.3O2的正极复合活性物质代替水合正磷酸铬(CrPO4·7/2H2O)包覆LiNi0.5Co0.2Mn0.3O2的正极复合活性物质，其中，一水合正磷酸镍(NiPO4·H2O)包覆LiNi0.5Co0.2Mn0.3O2的正极复合活性物质按如下方法制备：
将2910g六水硝酸亚镍用20000g去离子水溶解，制得硝酸亚镍溶液，将1640g无水磷酸三钠用16000g去离子水溶解，得到磷酸三钠溶液。在搅拌的条件下，将上述两种溶液混合，并用质量分数为65％的浓硝酸调节混合体系pH值为3，控制混合时间为2小时，得到悬浮液。然后将该悬浮液转移至水热反应釜，在搅拌的条件下，180℃热处理10小时，得到沉淀。将该沉淀用去离子水洗涤以去除其中的钠离子和磷酸根，真空抽滤后得到均匀的滤饼L22，取100g L22，用无水乙醇置换其中的水，然后在空气气氛下，100℃热处理5小时，得到干燥的固体，测得其重量为26.64g，由此推算滤饼L22固含量为26.64％。将作为活性成分的1000g化学式为LiNi0.5Co0.2Mn0.3O2的锂镍钴锰氧正极材料加入344g滤饼L22中，加入1500g去离子水，240rpm下强力搅拌5小时，110℃下喷雾干燥，得到一水合正磷酸镍(NiPO4·H2O)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8.4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，用水合正磷酸铋(BiPO4·2/3H2O)包覆LiNi0.5Co0.2Mn0.3O2的正极复合活性物质代替水合正磷酸铬(CrPO4·7/2H2O)包覆LiNi0.5Co0.2Mn0.3O2的正极复合活性物质，其中，水合正磷酸铋(BiPO4·2/3H2O)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，将1640g无水磷酸三钠用16000g去离子水溶解，得到磷酸三钠溶液。在搅拌的条件下，将上述两种溶液混合，并用质量分数为85％的浓磷酸调节混合体系pH值为5，控制混合时间为2小时，得到悬浮液。然后将该悬浮液转移至水热反应釜，在搅拌的条件下，180℃热处理10小时，得到沉淀。将该沉淀用去离子水洗涤以去除其中的钠离子和磷酸根，真空抽滤后得到均匀的滤饼L23，取100g L23，用无水乙醇置换其中的水，然后在空气气氛下，100℃热处理5小时，得到干燥的固体，测得其重量为30.44g，由此推算滤饼L23固含量为30.44％。将作为活性成分的1000g化学式为LiNi0.5Co0.2Mn0.3O2的锂镍钴锰氧正极材料加入301g滤饼L23中，加入1500g去离子水，220rpm下强力搅拌5小时，110℃下喷雾干燥，得到水合正磷酸铋(BiPO4·2/3H2O)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8.4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，用三水合磷酸铜(归一化通式为Cu(PO4)2/3·H2O)包覆LiNi0.5Co0.2Mn0.3O2的正极复合活性物质代替水合正磷酸铬(CrPO4·7/2H2O)包覆LiNi0.5Co0.2Mn0.3O2的正极复合活性物质，其中，三水合磷酸铜(归一化通式为Cu(PO4)2/3·H2O)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，将1093g无水磷酸三钠用10000g去离子水溶解，得到磷酸三钠溶液。在搅拌的条件下，将上述两种溶液混合，控制混合时间为2小时，得到悬浮液。然后将该悬浮液转移至水热反应釜，在搅拌的条件下，180℃热处理10小时，得到沉淀。将该沉淀用去离子水洗涤以去除其中的钠离子和磷酸根，真空抽滤后得到均匀的滤饼L24，取100g L24，用无水乙醇置换其中的水，然后在空气气氛下，100℃热处理5小时，得到干燥的固体，测得其重量为28.80g，由此推算滤饼L24固含量为28.80％。将作为活性成分的1000g化学式为LiNi0.5Co0.2Mn0.3O2的锂镍钴锰氧正极材料加入318g滤饼L24中，加入1500g去离子水，210rpm下强力搅拌5小时，110℃下喷雾干燥，得到三水合磷酸铜(归一化通式为Cu(PO4)2/3·H2O)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8.4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，用二水合磷酸锌(归一化通式为Zn(PO4)2/3·2/3H2O)包覆LiNi0.5Co0.2Mn0.3O2的正极复合活性物质代替水合正磷酸铬(CrPO4·7/2H2O)包覆LiNi0.5Co0.2Mn0.3O2的正极复合活性物质，其中，二水合磷酸锌(归一化通式为Zn(PO4)2/3·2/3H2O)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，将1093g无水磷酸三钠用10000g去离子水溶解，得到磷酸三钠溶液。在搅拌的条件下，将上述两种溶液混合，控制混合时间为2小时，得到悬浮液。然后将该悬浮液转移至水热反应釜，在搅拌的条件下，180℃热处理10小时，得到沉淀。将该沉淀用去离子水洗涤以去除其中的钠离子和磷酸根，真空抽滤后得到均匀的滤饼L25，取100g L25，用无水乙醇置换其中的水，然后在空气气氛下，100℃热处理5小时，得到干燥的固体，测得其重量为29.26g，由此推算滤饼L25固含量为29.26％。将作为活性成分的1000g化学式为LiNi0.5Co0.2Mn0.3O2的锂镍钴锰氧正极材料加入313g滤饼L25中，加入1500g去离子水，230rpm下强力搅拌5小时，110℃下喷雾干燥，得到二水合磷酸锌(归一化通式为Zn(PO4)2/3·2/3H2O)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8.4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312.1g/m2(电池中正极锂镍钴锰氧活性成分的重量与实施例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312.1g/m2(电池中正极锂镍钴铝氧活 性成分的重量与实施例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312.1g/m2(电池中正极钴酸锂活性成分的重量与实施例3相同)。
对比例4
按照实施例1的方法制备锂离子电池D4，不同的是，用正磷酸铬(CrPO4，不含结晶水)包覆LiNi0.5Co0.2Mn0.3O2的正极复合活性物质代替水合正磷酸铬(CrPO4·7/2H2O)包覆LiNi0.5Co0.2Mn0.3O2的正极复合活性物质，其中，正磷酸铬(CrPO4，不含结晶水)包覆LiNi0.5Co0.2Mn0.3O2的正极复合活性物质按如下方法制备：
将4000g九水硝酸铬用20000g去离子水溶解，制得硝酸铬溶液，将1640g无水磷酸三钠用16000g去离子水溶解，得到磷酸三钠溶液。在搅拌的条件下，将上述两种溶液混合，并用质量分数为85％的浓磷酸调节混合体系pH值为5，控制混合时间为2小时，得到悬浮液。然后将该悬浮液转移至水热反应釜，在搅拌的条件下，180℃热处理10小时，得到沉淀。将该沉淀用去离子水洗涤以去除其中的钠离子和磷酸根，真空抽滤后得到均匀的滤饼L26，取100g L26，用无水乙醇置换其中的水，然后在空气气氛下，500℃热处理8小时，得到干燥的固体，测得其重量为25.88g，由此推算滤饼L26中正磷酸铬(CrPO4，不含结晶水)含量为25.88％。将作为活性成分的1000g化学式为LiNi0.5Co0.2Mn0.3O2的锂镍钴锰氧正极材料加入354g滤饼L26中，加入1500g去离子水，290rpm下强力搅拌5小时，110℃下喷雾干燥，然后在空气气氛下，500℃热处理8小时，得到正磷酸铬(CrPO4，不含结晶水)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，正磷酸铬(CrPO4，不含结晶水)的含量为8.4重量％)。
对比例5
按照实施例2的方法制备锂离子电池D5，不同的是，用正磷酸亚钴(归一化通式为Co(PO4)2/3，不含结晶水)包覆LiNi0.8Co0.15Al0.05O2的正极复合活性物质代替八水合正磷酸亚钴(归一化通式为Co(PO4)2/3·8/3H2O)包覆LiNi0.8Co0.15Al0.05O2的正极复合活性物质，其中，正磷酸亚钴(归一化通式为Co(PO4)2/3，不含结晶水)包覆LiNi0.8Co0.15Al0.05O2的正极复合活性物质按如下方法制备：
将2910g六水硝酸亚钴用15000g去离子水溶解，制得硝酸亚钴溶液，将1093g无水磷酸三钠用10000g去离子水溶解，得到磷酸三钠溶液。在搅拌及氮气保护的条件下，将上述两种溶液混合，控制混合时间为2小时，得到悬浮液。然后将该悬浮液转移至水热反应釜，在搅拌及氮气保护的条件下，180℃热处理10小时，得到沉淀。将该沉淀用去离子水洗涤以去除其中的钠离子和磷酸根，真空抽滤后得到均匀的滤饼L27，取100g L27，用无水乙醇置换其中的水，然后在氮气气氛下，500℃热处理8小时，得到干燥的固体，测得其重量为19.57g，由此推算滤饼L27中正磷酸亚钴(归一化通式为Co(PO4)2/3，不含结晶水)含量为19.57％。将作为活性成分的1000gLiNi0.8Co0.15Al0.05O2锂镍钴铝氧加入469g滤饼L27中，加入1500g去离子水，氮气气氛下，320rpm下强力搅拌5小时，110℃下喷雾干燥，然后在氮气气氛下，500℃热处理8小时，得到正磷酸亚钴(归一化通式为Co(PO4)2/3，不含结晶水)包覆LiNi0.8Co0.15Al0.05O2锂镍钴铝氧的正极复合活性物质(以复合活性物质的重量为基准，正磷酸亚钴(归一化通式为Co(PO4)2/3，不含结晶水)的含量为8.4重量％)。
对比例6
按照实施例3的方法制备锂离子电池D6，不同的是，用磷酸镁(归一化通式为Mg(PO4)0.6(HPO4)0.1，不含结晶水)包覆钴酸锂LiCoO2的正极复合活性物质代替水合磷酸镁(归一化通式为Mg(PO4)0.6(HPO4)0.1·3/2H2O)包覆LiCoO2的正极复合活性物质，其中，磷酸镁(归一化通式 为Mg(PO4)0.6(HPO4)0.1，不含结晶水)包覆钴酸锂LiCoO2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，将984g无水磷酸三钠、358g十二水合磷酸氢二钠用10000g去离子水溶解，得到磷酸三钠、磷酸氢二钠混合溶液。在搅拌的条件下，将硝酸镁溶液与磷酸三钠、磷酸氢二钠混合溶液混合，控制混合时间为2小时，得到悬浮液。然后将该悬浮液转移至水热反应釜，在搅拌的条件下，180℃热处理10小时，得到沉淀。将该沉淀用去离子水洗涤以去除其中的钠离子和磷酸根，真空抽滤后得到均匀的滤饼L28，取100g L28，用无水乙醇置换其中的水，然后在空气气氛下，500℃热处理5小时，得到干燥的固体，测得其重量为19.24g，由此推算滤饼L28中磷酸镁(归一化通式为Mg(PO4)0.6(HPO4)0.1，不含结晶水)含量为19.24％。将作为活性成分的1000g钴酸锂LiCoO2正极材料加入477g滤饼L28中，加入1500g去离子水，350rpm下强力搅拌5小时，110℃下喷雾干燥，然后在空气气氛下，500℃热处理8小时，得到磷酸镁(归一化通式为Mg(PO4)0.6(HPO4)0.1，不含结晶水)包覆钴酸锂LiCoO2的正极复合活性物质(以复合活性物质的重量为基准，磷酸镁(归一化通式为Mg(PO4)0.6(HPO4)0.1，不含结晶水)的含量为8.4重量％)。
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1-25制得的锂离子电池A1-A25以及对比例1-6制得的锂离子电池D1-D6)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1-25制得的锂离子电池A1-A25以及对比例1-6制得的锂离子电池D1-D6)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1-25制得的锂离子电池A1-A25以及对比例1-6制得的锂离子电池D1-D6)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1-25制得的锂离子电池A1-A25以及对比例1-6制得的锂离子电池D1-D6)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 PCTCN2017074515-appb-000001
Figure PCTCN2017074515-appb-000002
表2
Figure PCTCN2017074515-appb-000003
Figure PCTCN2017074515-appb-000004
表3
Figure PCTCN2017074515-appb-000005
Figure PCTCN2017074515-appb-000006
表4
Figure PCTCN2017074515-appb-000007
Figure PCTCN2017074515-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所述的由水合磷酸盐添加剂包覆活性物质得到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，且引入的添加剂中必须含有结晶水，当引入不含结晶水的相应物质时，在滥用条件下，相应物质无法有效吸收电池热量，因而起不到明显提高电池安全性的作用。
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5.6-10.6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10-25的结果比较可知，所述添加剂为水合正磷酸铬(CrPO4·7/2H2O)、八水合正磷酸亚钴(归一化通式为Co(PO4)2/3·8/3H2O)和水合磷酸镁(归一化通式为Mg(PO4)0.6(HPO4)0.1·3/2H2O)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(PO4)a(HPO4)b·cH2O，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、VIB族金属元素、VIIB族金属元素、VIII族金属元素和VA族金属元素中的至少一种元素，a≥0，b≥0，且a，b不同时为0，c>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VIB族金属元素为Cr，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VA族金属元素为Bi；
    优选地，所述添加剂为CrPO4·7/2H2O、Co(PO4)2/3·8/3H2O和Mg(PO4)0.6(HPO4)0.1·3/2H2O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0.05-32重量％，优选为3-15重量％，进一步优选为5.6-10.6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的水合磷酸盐，在分散剂存在下，将所述元素M的水合磷酸盐与活性物质混合，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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