CN105161710A - Battery cathode material, preparation method thereof and lithium ion battery - Google Patents

Battery cathode material, preparation method thereof and lithium ion battery Download PDF

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Publication number
CN105161710A
CN105161710A CN201510548352.5A CN201510548352A CN105161710A CN 105161710 A CN105161710 A CN 105161710A CN 201510548352 A CN201510548352 A CN 201510548352A CN 105161710 A CN105161710 A CN 105161710A
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cell positive
formula
oxide
nickel cobalt
positive material
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Inventor
毛秦钟
佘圣贤
黄连友
陈炼
袁徐俊
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NINGBO JINHE LITHIUM BATTERY MATERIAL Co Ltd
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NINGBO JINHE LITHIUM BATTERY MATERIAL Co Ltd
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Priority to CN201510548352.5A priority Critical patent/CN105161710A/en
Publication of CN105161710A publication Critical patent/CN105161710A/en
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
    • H01M4/502—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese for non-aqueous cells
    • 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
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/483—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides for non-aqueous cells
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/485—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
    • H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
    • H01M4/523—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron for non-aqueous cells
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
    • H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Abstract

The invention provides a battery cathode material. The battery cathode material comprises a single-crystal structurized substrate and a coating layer, wherein the coating layer coats the surface of the substrate and is aluminum oxide or zirconium oxide. The battery cathode material provided by the invention comprises the single-crystal structurized substrate; by the single-crystal structurized substrate, particle breakage caused by positive sheet grinding during the battery fabrication process can be prevented; and meanwhile, with the joint effects of a doping element in the battery cathode material and the coating layer, the structural stability of the cathode material can be improved, the corrosion of an electrolyte to the material is relieved, and a lithium ion battery prepared from the cathode material has favorable high-temperature cycle performance. The invention also provides a preparation method of the battery cathode material and the lithium ion battery.

Description

A kind of cell positive material and preparation method thereof and lithium ion battery
Technical field
The present invention relates to cell art, particularly relate to a kind of cell positive material and preparation method thereof and lithium ion battery.
Background technology
Nickle cobalt lithium manganate (NCM) ternary material, there is higher reversible capacity (theoretical capacity reaches 274mAh/g), excellent security performance and lower price, receive the extensive concern of researcher, but the poor under the high temperature conditions cycle performance of this material limits its application on electric automobile direction.
Nearest research shows, NCM ternary material is in the tableting processes preparing battery, cause NCM material secondary particle ball easily cracked because pole piece rolls, destroy the surface texture of material, and NCM ternary material in cyclic process due to the stripping of its metal ion, further can destroy material surface structure; Thus the lithium ion battery causing NCM material to prepare produces decay in the process of high temperature circulation.The current material that improves causes the method for cracked problem to be carry out the blending of size particles owing to rolling, and improves the bulk density of material itself, increase its anti-pressure ability, but this method still exists the cracked problem of local granule; The method of current solution digestion of metallic ion is at NCM top layer coated metal oxide, alleviate electrolyte to the corrosion of active material, but the stripping of this method metal ion that the structure collapses of the NCM material at high temperature long circulating process itself cannot be suppressed to cause.
Therefore, what prior art urgent need solution positive electrode produced in preparation cell process rolls Crushing Problem, and improve cathode material structure stability and prevent electrolyte to the etching problem of positive electrode, prior art needs a kind of new positive electrode, and lithium ion battery prepared by this positive electrode has good high temperature cyclic performance.
Summary of the invention
In view of this, the object of the present invention is to provide a kind of cell positive material and preparation side thereof and lithium ion battery, the lithium ion battery that cell positive material provided by the invention prepares has good high temperature cyclic performance.
The invention provides a kind of cell positive material, comprise the base material of mono-crystalline structures, described base material is the compound shown in formula I:
LiNi xco ymn (1-x-y)y ao 2formula I;
In formula I, 0 < x < 0.6,0 < y < 1.0,0 < x+y < 1.0,0 < a < 0.1;
Y is one or more in Mg, Ti, Zr, Sr and Al;
Be coated on the coating layer of described substrate surface, described coating layer is aluminium oxide or zirconia.
Preferably, containing multiple single crystal grain in the base material of described mono-crystalline structures, the granularity of described single crystal grain is 0.5 micron ~ 5 microns.
Preferably, the granularity of the base material of described mono-crystalline structures is 3 microns ~ 8 microns.
Preferably, the thickness of described coating layer is 1 nanometer ~ 50 nanometer.
Preferably, the quality of described coating layer is 0.04% ~ 2% of described cell positive material quality.
Cell positive material provided by the invention comprises the base material of mono-crystalline structures, the positive electrode of this mono-crystalline structures can prevent from preparing positive plate in the process of battery and roll the Particle Breakage caused, simultaneously by the acting in conjunction of the doped chemical in cell positive material and coating layer, can improve the structural stability of positive electrode and alleviate the corrosion of electrolyte to material, lithium ion battery prepared by this positive electrode has good high temperature cyclic performance.Experimental result shows, full battery 60 DEG C of 100 circulation volume conservation rates prepared by cell positive material provided by the invention are 96.3% ~ 97.2%.
The invention provides the preparation method of the cell positive material described in a kind of technique scheme, comprising:
Be incubated after the oxide and lithium salts with the nickel cobalt manganese of mono-crystalline structures are carried out the first calcining, obtain intermediate product, the temperature of described first calcining is 500 DEG C ~ 800 DEG C; The oxide of described nickel cobalt manganese is the compound shown in formula II:
Ni xco ymn (1-x-y)m ao 2formula II;
Be incubated after described intermediate product is carried out the second calcining, obtain the base material of mono-crystalline structures, the temperature of described second calcining is 801 DEG C ~ 1100 DEG C;
Described base material is the compound shown in formula I:
LiNi xco ymn (1-x-y)m ao 2formula I;
In formula I and formula II, 0 < x < 0.6,0 < y < 1.0,0 < x+y < 1.0,0 < a < 0.1;
M is one or more in Mg, Ti, Zr, Sr and Al;
Carry out heat treated by after the mixing of the oxide of described base material and coated element, obtain cell positive material; Described coated element is aluminium or zirconium.
Preferably, the preparation method described in the oxide of the nickel cobalt manganese of mono-crystalline structures is:
The mixed solution of nickel salt, manganese salt, cobalt salt and M salt is carried out coprecipitation reaction, obtain the hydroxide of nickel cobalt manganese, described M is one or more in Mg, Ti, Zr, Sr and Al, and the pH value of described coprecipitation reaction is 10 ~ 14, and the hydroxide of described nickel cobalt manganese is the compound shown in formula III:
Ni xco ymn (1-x-y)m a(OH) 2formula III;
In formula III, 0 < x < 0.6,0 < y < 1.0,0 < x+y < 1.0,0 < a < 0.1;
M is one or more in Mg, Ti, Zr, Sr and Al;
Sintered by the hydroxide of described nickel cobalt manganese, obtain the oxide of the nickel cobalt manganese of concrete mono-crystalline structures, the temperature of described sintering is 300 DEG C ~ 700 DEG C.
Preferably, the granularity of the oxide of described coated element is 5 nanometer ~ 100 nanometers.
Preferably, the temperature of described heat treated is 300 DEG C ~ 800 DEG C.
The preparation method of cell positive material provided by the invention adopts the Preparation base material with the nickel cobalt manganese of mono-crystalline structures, makes the base material for preparing and cell positive material also be mono-crystalline structures; The positive electrode of this mono-crystalline structures can prevent from preparing positive plate in the process of battery and roll the Particle Breakage caused; And preparation method provided by the invention carries out coated on the surface of base material, by carrying out coated acting in conjunction outside doped chemical in base material and base material, improve the structural stability of positive electrode and alleviate the corrosion of electrolyte to material, lithium ion battery prepared by the cell positive material that method provided by the invention is prepared has good high temperature cyclic performance.
The invention provides a kind of lithium ion battery, the positive electrode of described lithium ion battery is the cell positive material described in technique scheme, or the cell positive material that the method described in technique scheme prepares.
Lithium ion battery provided by the invention adopts the cell positive material described in technique scheme to prepare, above-mentioned cell positive material is mono-crystalline structures, and containing doped chemical and coating layer, lithium ion battery prepared by this cell positive material has good high temperature cyclic performance.
Accompanying drawing explanation
In order to be illustrated more clearly in the embodiment of the present invention or technical scheme of the prior art, be briefly described to the accompanying drawing used required in embodiment or description of the prior art below, apparently, accompanying drawing in the following describes is only embodiments of the invention, for those of ordinary skill in the art, under the prerequisite not paying creative work, other accompanying drawing can also be obtained according to the accompanying drawing provided.
Fig. 1 is the scanning electron microscope diagram of the oxide of the nickel cobalt manganese that the embodiment of the present invention 1 prepares;
Fig. 2 is the scanning electron microscope diagram of the cell positive material that the embodiment of the present invention 1 prepares;
Fig. 3 is the transmission electron microscope figure of the cell positive material that the embodiment of the present invention 1 prepares;
Fig. 4 is the scanning electron microscope diagram of the cell positive material that comparative example 1 of the present invention prepares.
Embodiment
Below in conjunction with the accompanying drawing in the embodiment of the present invention, be clearly and completely described the technical scheme in the embodiment of the present invention, obviously, described embodiment is only the present invention's part embodiment, instead of whole embodiments.Based on the embodiment in the present invention, those of ordinary skill in the art, not making the every other embodiment obtained under creative work prerequisite, belong to the scope of protection of the invention.
The invention provides a kind of cell positive material, comprise the base material of mono-crystalline structures, described base material is the compound shown in formula I:
LiNi xco ymn (1-x-y)y ao 2formula I;
In formula I, 0 < x < 0.6,0 < y < 1.0,0 < x+y < 1.0,0 < a < 0.1;
Y is one or more in Mg, Ti, Zr, Sr and Al;
Be coated on the coating layer of described substrate surface, described coating layer is aluminium oxide or zirconia.
Cell positive material provided by the invention comprises the base material of mono-crystalline structures, and described base material is the compound shown in formula I.In an embodiment of the present invention, in described formula I, 0.1 < x < 0.5; In other examples, in described formula I, 0.2 < x < 0.4.In an embodiment of the present invention, in described formula I, 0.1 < y < 0.9; In other examples, in described formula I, 0.3 < y < 0.7; In a further embodiment, in described formula I, 0.4 < y < 0.6.In an embodiment of the present invention, in described formula I, 0.1 < x+y < 0.9; In other examples, in described formula I, 0.3 < x+y < 0.7; In a further embodiment, in described formula I, 0.4 < x+y < 0.6.In an embodiment of the present invention, in described formula I, 0.01 < a < 0.09; In other examples, in described formula I, 0.03 < a < 0.07; In a further embodiment, in described formula I, 0.04 < a < 0.06.
In an embodiment of the present invention, in described formula I, Y is several in Mg, Ti, Zr, Sr and Al.In the present invention, the conductance of cell positive material provided by the invention can be improved when Y is Mg, Ti, improve the high rate performance of material; The stability of cell positive material mono-crystalline structures provided by the invention can be improved when Y is Zr, Sr, make positive electrode have good high-temperature behavior; When Y is Co, Al 3+atomic radius and Co 3+atomic radius relatively, the stability of cell positive material provided by the invention can be improved, make positive electrode have good cycle performance.
In an embodiment of the present invention, to be grown up the identical single crystal grain of the crystal orientation that formed by single particle containing multiple in the base material of described mono-crystalline structures, the granularity of described single crystal grain is 0.5 micron ~ 5 microns; In other examples, the granularity of described single crystal grain is 1 micron ~ 4 microns; In a further embodiment, the granularity of described single crystal grain is 2 microns ~ 3 microns.In an embodiment of the present invention, the granularity of the base material of described mono-crystalline structures is 3 microns ~ 8 microns; In other examples, the granularity of the base material of described mono-crystalline structures is 4 microns ~ 6 microns.
Cell positive material provided by the invention comprises the coating layer being coated on described substrate surface, and described coating layer is aluminium oxide or zirconia.In an embodiment of the present invention, the thickness of described coating layer is 1 nanometer ~ 50 nanometer; In other examples, the thickness of described coating layer is 10 nanometer ~ 40 nanometers; In a further embodiment, the thickness of described coating layer is 20 nanometer ~ 30 nanometers.
Of the present invention be in embodiment, the quality of described coating layer is 0.04% ~ 2% of described cell positive material quality; In other examples, the quality of described coating layer is 0.1% ~ 1.5% of described cell positive material quality; In a further embodiment, the quality of described coating layer is 0.5% ~ 1% of described cell positive material quality.In an embodiment of the present invention, make cell positive material provided by the invention have stable structure and the corrosion of electrolyte to positive electrode can be alleviated by the mass content controlling coating layer, cell positive material provided by the invention can also be made to have good compacted density and high rate performance simultaneously.
The invention provides the preparation method of the cell positive material described in a kind of technique scheme, comprising:
Be incubated after the oxide and lithium salts with the nickel cobalt manganese of mono-crystalline structures are carried out the first calcining, obtain intermediate product, the temperature of described first calcining is 500 DEG C ~ 800 DEG C; The oxide of described nickel cobalt manganese is the compound shown in formula II:
Ni xco ymn (1-x-y)m ao 2formula II;
Be incubated after described intermediate product is carried out the second calcining, obtain the base material of mono-crystalline structures, the temperature of described second calcining is 801 DEG C ~ 1100 DEG C;
Described base material is the compound shown in formula I:
LiNi xco ymn (1-x-y)m ao 2formula I;
In formula I and formula II, 0 < x < 0.6,0 < y < 1.0,0 < x+y < 1.0,0 < a < 0.1;
M is one or more in Mg, Ti, Zr, Sr and Al;
Carry out heat treated by after the mixing of the oxide of described base material and coated element, obtain cell positive material; Described coated element is aluminium or zirconium.
The present invention is incubated after the oxide and lithium salts with the nickel cobalt manganese of mono-crystalline structures are carried out the first calcining, obtains intermediate product, and the temperature of described first calcining is 500 DEG C ~ 800 DEG C.In an embodiment of the present invention, the temperature of described first calcining is 550 DEG C ~ 750 DEG C; In other examples, the temperature of described first calcining is 600 DEG C ~ 700 DEG C.In an embodiment of the present invention, carry out calcining rear insulation after the oxide of nickel cobalt manganese and lithium salts can being warming up to the first calcining heat with the programming rate of 0.5 DEG C/min ~ 5.0 DEG C/min, obtain intermediate product.In an embodiment of the present invention, described programming rate be 1 DEG C/min ~ 4 DEG C/min; In other examples, described programming rate be 2 DEG C/min ~ 3 DEG C/min.
In an embodiment of the present invention, after described first calcining, the time of insulation is 4 hours ~ 10 hours; In other examples, after described first calcining, the time of insulation is 6 hours ~ 8 hours.
In the present invention, the oxide of described nickel cobalt manganese is the compound shown in formula II, and have mono-crystalline structures, x, y, a in formula II are consistent with x, y, a and the M in formula I described in technique scheme with M, do not repeat them here.In an embodiment of the present invention, the pattern of the oxide of described nickel cobalt manganese is needle-like interference type arrangement, and the oxide of the nickel cobalt manganese of this pattern is conducive to the base material that form mono-crystalline structures rear with lithium compound calcining.
In an embodiment of the present invention, the preparation method of the oxide of the nickel cobalt manganese of described concrete mono-crystalline structures is:
The mixed solution of nickel salt, manganese salt, cobalt salt and M salt is carried out coprecipitation reaction, obtain the hydroxide of nickel cobalt manganese, described M is one or more in Mg, Ti, Zr, Sr and Al, and the pH value of described coprecipitation reaction is 10 ~ 14, and the hydroxide of described nickel cobalt manganese is the compound shown in formula III:
Ni xco ymn (1-x-y)m a(OH) 2formula III;
In formula III, 0 < x < 0.6,0 < y < 1.0,0 < x+y < 1.0,0 < a < 0.1;
M is one or more in Mg, Ti, Zr, Sr and Al;
Sintered by the hydroxide of described nickel cobalt manganese, obtain the oxide of the nickel cobalt manganese of concrete mono-crystalline structures, the temperature of described sintering is 300 DEG C ~ 700 DEG C.
In an embodiment of the present invention, by controlling the pH value in coprecipitation reaction process, and the temperature of adulterate in coprecipitation process M element and control sintering, prepare the oxide of the nickel cobalt manganese of mono-crystalline structures.
In an embodiment of the present invention, the mixed solution of nickel salt, manganese salt, cobalt salt and M salt is carried out coprecipitation reaction, obtains the oxyhydroxide of nickel cobalt manganese.In the present invention, the pH value of described coprecipitation reaction is 10 ~ 14.In an embodiment of the present invention, by the mixed solution of nickel salt, manganese salt and cobalt salt and M salting liquid and stream add and carry out coprecipitation reaction, obtain the hydroxide of nickel cobalt manganese.In an embodiment of the present invention, the pH value of described coprecipitation reaction is 12 ~ 13.In an embodiment of the present invention, the temperature of described coprecipitation reaction is 30 DEG C ~ 60 DEG C; In other examples, the temperature of described coprecipitation reaction is 40 DEG C ~ 50 DEG C.In an embodiment of the present invention, the time of described coprecipitation reaction is 12 hours ~ 48 hours; In other examples, the time of described coprecipitation reaction is 20 hours ~ 40 hours; In a further embodiment, the time of described coprecipitation reaction is 25 hours ~ 35 hours.
In an embodiment of the present invention, described nickel salt is one or more in the sulfate of nickel, nitrate and chlorate; In other examples, described nickel salt is the sulfate of nickel, nitrate or chlorate.In an embodiment of the present invention, described manganese salt is one or more in the sulfate of manganese, nitrate and chlorate; In other examples, described manganese salt is the sulfate of manganese, nitrate or chlorate.In an embodiment of the present invention, described cobalt salt is one or more in the sulfate of cobalt, nitrate and chlorate; In other examples, described cobalt salt is the sulfate of cobalt, nitrate or chlorate.In an embodiment of the present invention, described M salt is one or more in the sulfate of M, nitrate and chlorate; In other examples, described M salt is the sulfate of M, nitrate or chlorate.In the present invention, described M is consistent with M described in technique scheme, does not repeat them here.
In an embodiment of the present invention, in the mixed solution of described nickel salt, manganese salt, cobalt salt and Y salt, the mol ratio of nickel, cobalt, manganese and M is x:y:(1-x-y): a, 0 < x < 0.6,0 < y < 1.0,0 < x+y < 1.0,0 < a < 0.1.In the present invention, described x, y are consistent with x, y and a described in technique scheme with a, do not repeat them here.
In an embodiment of the present invention, the molar concentration that in the mixed solution of described nickel salt, manganese salt, cobalt salt and M salt, nickel, cobalt and manganese are total is 0.5mol/L ~ 4mol/L; In other examples, the molar concentration that in the mixed solution of described nickel salt, manganese salt, cobalt salt and M salt, nickel, cobalt and manganese are total is 1mol/L ~ 3mol/L; In a further embodiment, the molar concentration that in the mixed solution of described nickel salt, manganese salt, cobalt salt and M salt, nickel, cobalt and manganese are total is 1.5mol/L ~ 2.5mol/L.In an embodiment of the present invention, the molar concentration of described M salting liquid is 0.1mol/L ~ 2mol/L; In other examples, the molar concentration of described M salting liquid is 0.5mol/L ~ 1.5mol/L; In a further embodiment, the molar concentration of described M salting liquid is 0.8mol/L ~ 1.2mol/L.
In an embodiment of the present invention, after described coprecipitation reaction completes, by the product washing obtained, filter and drying, obtain the hydroxide of nickel cobalt manganese.
In an embodiment of the present invention, the hydroxide of described nickel cobalt manganese is the compound shown in formula III, and x, y, a in described formula III are consistent with x, y, a and the M in the formula I described in technique scheme with M, do not repeat them here.In an embodiment of the present invention, the granularity of the hydroxide of described nickel cobalt manganese is 0.5 micron ~ 5 microns; In other examples, the granularity of the hydroxide of described nickel cobalt manganese is 1 micron ~ 4 microns; In a further embodiment, the granularity of the hydroxide of described nickel cobalt manganese is 2 microns ~ 3 microns.
In an embodiment of the present invention, after obtaining the hydroxide of nickel cobalt manganese, the hydroxide of described nickel cobalt manganese sinters by the present invention, obtains the oxide of nickel cobalt manganese.In an embodiment of the present invention, the temperature of described sintering is 300 DEG C ~ 700 DEG C; In other examples, the temperature of described sintering is 400 DEG C ~ 600 DEG C; In a further embodiment, the temperature of described sintering is 450 DEG C ~ 550 DEG C.In an embodiment of the present invention, the time of described sintering is 4 hours ~ 10 hours; In other examples, the time of described sintering is 6 hours ~ 8 hours.
In an embodiment of the present invention, described lithium salts comprises one or both in lithium carbonate and lithium hydroxide; In other examples, described lithium salts comprises lithium carbonate or lithium hydroxide.In an embodiment of the present invention, the ratio of the molal quantity of the described oxide of nickel cobalt manganese and the consumption of the lithium salts molal quantity that makes nickel, cobalt, manganese total and lithium is 1:(1.04 ~ 1.2); In other examples, the ratio of the molal quantity of the described oxide of nickel cobalt manganese and the consumption of the lithium salts molal quantity that makes nickel, cobalt, manganese total and lithium is 1:(1.08 ~ 1.1).
After obtaining intermediate product, the present invention is incubated after described intermediate product is carried out the second calcining, obtains the base material of mono-crystalline structures, and the temperature of described second calcining is 801 DEG C ~ 1100 DEG C.In an embodiment of the present invention, the temperature of described second calcining is 850 DEG C ~ 1000 DEG C; In other examples, the temperature of described second calcining is 900 DEG C ~ 950 DEG C.In an embodiment of the present invention, after described second calcining, the time of insulation is 6 hours ~ 20 hours; In other examples, after described second calcining, the time of insulation is 10 hours ~ 15 hours.
In the present invention, described base material is consistent with the base material described in technique scheme, does not repeat them here.
After obtaining the base material of mono-crystalline structures, the present invention carries out heat treated by after the mixing of the oxide of the base material of described mono-crystalline structures and coated element, obtains cell positive material.In an embodiment of the present invention, the method for the oxide mixing of the base material of described mono-crystalline structures and coated element can mix for ball milling, mixed at high speed or agravic mixing.In an embodiment of the present invention, the temperature of described heat treated is 300 DEG C ~ 800 DEG C; In other examples, the temperature of described heat treated is 400 DEG C ~ 700 DEG C; In a further embodiment, the temperature of described heat treated is 500 DEG C ~ 600 DEG C.In an embodiment of the present invention, the time of described heat treated is 4 hours ~ 10 hours; In other examples, the time of described heat treated is 6 hours ~ 8 hours.
In the present invention, in the oxide of described coated element, coated element is aluminium or zirconium.In an embodiment of the present invention, the granularity of the oxide of described coated element is nanoscale, and the granularity of the oxide of described coated element is 5 nanometer ~ 100 nanometers; In other examples, the granularity of the oxide of described coated element is 30 nanometer ~ 70 nanometers; In a further embodiment, the granularity of the oxide of described coated element is 40 nanometer ~ 60 nanometers.
In an embodiment of the present invention, the consumption of the oxide of described coated element makes the mass content of the oxide of coated element in the positive electrode prepared be 0.04% ~ 2%.
The invention provides a kind of lithium ion battery, the cell positive material that the positive electrode of lithium ion battery provided by the invention prepares for the cell positive material described in technique scheme or the method described in technique scheme.The positive electrode of lithium ion battery provided by the invention is the cell positive material described in technique scheme, above-mentioned cell positive material is mono-crystalline structures, and containing doped chemical and coating layer, lithium ion battery prepared by this cell positive material has good high temperature cyclic performance.
The preparation method of the present invention to described lithium ion battery does not have special restriction, adopts employing positive electrode well known to those skilled in the art to prepare the technical scheme of lithium ion battery, as prepared lithium ion battery by the following method:
Cell positive material provided by the invention, conductive agent, binding agent and 1-METHYLPYRROLIDONE (NMP) are mixed, obtains anode sizing agent; Described anode sizing agent is coated on aluminium foil, obtains positive plate;
Described positive plate, lithium ion battery negative, barrier film and electrolyte are assembled, prepares lithium ion battery.
In an embodiment of the present invention, described conductive agent is conductive black (Super-P).In an embodiment of the present invention, described binding agent is polyvinylidene fluoride copolymers thing, as HSV900.In an embodiment of the present invention, the mass ratio of described cell positive material, conductive agent, binding agent and NMP is (93 ~ 97): (2 ~ 3): (2 ~ 4): (65 ~ 75); In other examples, the mass ratio of described cell positive material, conductive agent, binding agent and NMP is (94 ~ 96): (2.4 ~ 2.6): (2.5 ~ 3.5): (68 ~ 72); In a further embodiment, the mass ratio of described cell positive material, conductive agent, binding agent and NMP is 94.5:2.5:3.0:70.In an embodiment of the present invention, described anode sizing agent is coated on after on aluminium foil and obtains positive plate by after aluminium foil drying, roll-in.
In an embodiment of the present invention, described lithium ion battery negative is Delanium.In an embodiment of the present invention, described barrier film is microporous polypropylene membrane, as cellgard2000.In an embodiment of the present invention, described electrolyte is LiPF 6solution.In an embodiment of the present invention, described LiPF 6the concentration of solution is 0.5mol/L ~ 1.5mol/L; In other examples, described LiPF 6the concentration of solution is 0.8mol/L ~ 1.2mol/L; In a further embodiment, described LiPF 6the concentration of solution is 1mol/L.In an embodiment of the present invention, described LiPF 6solvent in solution comprises ethylene carbonate (EC) and dimethyl carbonate (DMC).In an embodiment of the present invention, the volume ratio of described EC and DMC is 1:1.
Test the compacted density of cell positive material provided by the invention by the following method:
Be make slurry after the ratio uniform mixing of 94.5:2.5:3.0:70 according to mass ratio by cell positive material provided by the invention, Super-P conductive agent, HSV900 binding agent and 1-METHYLPYRROLIDONE (NMP); This slurry is spread evenly across on aluminium foil and makes pole piece; Dried by the pole piece obtained, roll-in calculates compacted density there is diaphanous spot after pole piece doubling till according to the following equation:
Cell positive material content in the compacted density=unit are/thickness-aluminum foil thickness of pole piece (after the roll-in);
Test result is, the compacted density of cell positive material provided by the invention is 3.71/gcm 3~ 3.78/gcm 3.
Battery is helped in positive electrode preparation provided by the invention, and concrete grammar is:
Be make anode sizing agent after the ratio uniform mixing of 94.5:2.5:3.0:70 according to mass ratio by cell positive material provided by the invention, Super-P conductive agent, HSV900 binding agent and 1-METHYLPYRROLIDONE (NMP); Described anode sizing agent is spread evenly across on aluminium foil and makes pole piece; By described pole piece oven dry, roll-in, obtain positive plate;
Described positive plate and Delanium are assembled into lithium ion battery, adopt microporous polypropylene membrane (cellgard2000) as lithium ion battery separator, with the ethylene carbonate of volume ratio 1:1 (EC) and dimethyl carbonate (DMC) for solvent, by LiPF 6be dissolved in solvent make 1mol/L solution as the electrolyte of lithium ion battery, prepare full battery;
Charge-discharge test is carried out after described full battery is at room temperature placed 24 hours.
Test the high temperature cyclic performance of above-mentioned full battery, under 60 DEG C of 3.0 ~ 4.2V voltage 1C discharge and recharge conditions, carry out loop test; Test result is, full battery 60 DEG C of 100 circulation volume conservation rates prepared by cell positive material provided by the invention are 96.3% ~ 97.2%.
Following examples of the present invention raw material used is commercial goods.
Embodiment 1
Be that the ratio of 1:1:1 is by soluble in water to cobaltous sulfate, nickelous sulfate, manganese sulfate according to the mol ratio of Ni, Co and Mn, be made into the mixed solution of 1mol/L, by the Titanium Nitrate aqueous solution of 0.1mol/L and above-mentioned mixed solution by respective pipeline and stream join in reactor and carry out coprecipitation reaction, the pH value controlling coprecipitation reaction is 11.2, the coprecipitation reaction product that obtains is stirred, washing, dry, obtain the Ni that D50 granularity is 3 μm 1/3co 1/3mn 1/3ti 0.01(OH) 2the hydroxide of nickel cobalt manganese;
The hydroxide of described nickel cobalt manganese is sintered 6h at 600 DEG C, obtains Ni 1/3co 1/3mn 1/3ti 0.01o 2the oxide of nickel cobalt manganese;
By the oxide of described nickel cobalt manganese and the mixing of lithium carbonate ball milling, the ratio of the molal quantity of the molal quantity that the described oxide of nickel cobalt manganese and the consumption of lithium carbonate make nickel, cobalt, manganese total and lithium is 1.1:1; The mixture obtained is warming up to 700 DEG C of insulation 4h with the speed of 3 DEG C/min, is then warming up to 1000 DEG C of insulation 12h, the product obtained is cooled naturally, obtains the LiNi that single crystal grain is 3 μm 1/3co 1/3mn 1/3ti 0.01o 2base material;
Be at 500 DEG C, be incubated 8 hours after the aluminium oxide of 30nm is mixed by the mode of ball milling by described base material and granularity, obtain cell positive material; In described cell positive material, the content of aluminium oxide is 0.2wt%.
Carry out scanning electron microscopy detection to the oxide of the nickel cobalt manganese that the embodiment of the present invention 1 prepares, as shown in Figure 1, Fig. 1 is the picture of the scanning electron microscopy of the oxide of the nickel cobalt manganese that the embodiment of the present invention 1 prepares to testing result.
Scanning electron microscopy detection and transmission electron microscope detection are carried out to the cell positive material that the embodiment of the present invention 1 prepares, testing result as shown in Figures 2 and 3, Fig. 2 is the scanning electron microscope diagram of the cell positive material that the embodiment of the present invention 1 prepares, and Fig. 3 is the transmission electron microscope figure of the cell positive material that the embodiment of the present invention 1 prepares.
Test compacted density and the high temperature cyclic performance of the cell positive material that the embodiment of the present invention 1 prepares according to the method described above, test result is as shown in table 1, and table 1 is the performance test results of the cell positive material that the embodiment of the present invention and comparative example prepare.
Embodiment 2
Be that the ratio of 5:2:3 is by soluble in water to cobaltous sulfate, nickelous sulfate, manganese sulfate according to the mol ratio of Ni, Co and Mn, be made into the mixed solution of 2mol/L, by the zirconium nitrate aqueous solution of 0.1mol/L and above-mentioned mixed solution by respective pipeline and stream join in reactor and carry out coprecipitation reaction, the pH value controlling coprecipitation reaction is 11, the coprecipitation reaction product that obtains is stirred, washing, dry, obtain the Ni that D50 granularity is 2.5 μm 0.5co 0.2mn 0.3zr 0.01(OH) 2the hydroxide of nickel cobalt manganese;
The hydroxide of described nickel cobalt manganese is sintered 6h at 600 DEG C, obtains Ni 0.5co 0.2mn 0.3zr 0.01o 2the oxide of nickel cobalt manganese;
By the oxide of described nickel cobalt manganese and the mixing of lithium carbonate ball milling, the ratio of the molal quantity of the molal quantity that the described oxide of nickel cobalt manganese and the consumption of lithium carbonate make nickel, cobalt, manganese total and lithium is 1.02:1; The mixture obtained is warming up to 700 DEG C of insulation 4h with the speed of 3 DEG C/min, is then warming up to 960 DEG C of insulation 12h, the product obtained is cooled naturally, obtains the LiNi that single crystal grain is 3.5 μm 0.5co 0.2mn 0.3zr 0.01o 2base material;
Be at 550 DEG C, be incubated 8 hours after the aluminium oxide of 30nm is mixed by the mode of ball milling by described base material and granularity, obtain cell positive material; In described cell positive material, the content of aluminium oxide is 1wt%.
Test compacted density and the high temperature cyclic performance of the cell positive material that the embodiment of the present invention 2 prepares according to the method described above, test result is as shown in table 1.
Embodiment 3
Be that the ratio of 5:2:3 is by soluble in water to cobaltous sulfate, nickelous sulfate, manganese sulfate according to the mol ratio of Ni, Co and Mn, be made into the mixed solution of 1.5mol/L, by the zirconium nitrate aqueous solution of 0.1mol/L and above-mentioned mixed solution by respective pipeline and stream join in reactor and carry out coprecipitation reaction, the pH value controlling coprecipitation reaction is 11, the coprecipitation reaction product that obtains is stirred, washing, dry, obtain the Ni that D50 granularity is 2.5 μm 0.5co 0.2mn 0.3zr 0.02(OH) 2the hydroxide of nickel cobalt manganese;
The hydroxide of described nickel cobalt manganese is sintered 6h at 600 DEG C, obtains Ni 0.5co 0.2mn 0.3zr 0.02o 2the oxide of nickel cobalt manganese;
By the oxide of described nickel cobalt manganese and the mixing of lithium carbonate ball milling, the ratio of the molal quantity of the molal quantity that the described oxide of nickel cobalt manganese and the consumption of lithium carbonate make nickel, cobalt, manganese total and lithium is 1.06:1; The mixture obtained is warming up to 700 DEG C of insulation 4h with the speed of 3 DEG C/min, is then warming up to 955 DEG C of insulation 10h, the product obtained is cooled naturally, obtains the LiNi that single crystal grain is 4 μm 0.5co 0.2mn 0.3zr 0.02o 2base material;
Be at 580 DEG C, be incubated 8 hours after the aluminium oxide of 30nm is mixed by the mode of ball milling by described base material and granularity, obtain cell positive material; In described cell positive material, the content of aluminium oxide is 0.5wt%.
Test compacted density and the high temperature cyclic performance of the cell positive material that the embodiment of the present invention 3 prepares according to the method described above, test result is as shown in table 1.
Embodiment 4
Be that the ratio of 5:2:3 is by soluble in water to cobaltous sulfate, nickelous sulfate, manganese sulfate according to the mol ratio of Ni, Co and Mn, be made into the mixed solution of 1.5mol/L, by the magnesium nitrate aqueous solution of 0.5mol/L and above-mentioned mixed solution by respective pipeline and stream join in reactor and carry out coprecipitation reaction, the pH value controlling coprecipitation reaction is 11.2, the coprecipitation reaction product that obtains is stirred, washing, dry, obtain the Ni that D50 granularity is 3 μm 0.5co 0.2mn 0.3mg 0.02(OH) 2the hydroxide of nickel cobalt manganese;
The hydroxide of described nickel cobalt manganese is sintered 6h at 600 DEG C, obtains Ni 0.5co 0.2mn 0.3mg 0.02o 2the oxide of nickel cobalt manganese;
By the oxide of described nickel cobalt manganese and the mixing of lithium carbonate ball milling, the ratio of the molal quantity of the molal quantity that the described oxide of nickel cobalt manganese and the consumption of lithium carbonate make nickel, cobalt, manganese total and lithium is 1.08:1; The mixture obtained is warming up to 700 DEG C of insulation 4h with the speed of 3 DEG C/min, is then warming up to 930 DEG C of insulation 10h, the product obtained is cooled naturally, obtains the LiNi that single crystal grain is 3 μm 0.5co 0.2mn 0.3mg 0.02o 2base material;
Be at 580 DEG C, be incubated 8 hours after the zirconia of 20nm is mixed by the mode of ball milling by described base material and granularity, obtain cell positive material; In described cell positive material, zirconic content is 0.2wt%.
Test compacted density and the high temperature cyclic performance of the cell positive material that the embodiment of the present invention 4 prepares according to the method described above, test result is as shown in table 1.
Comparative example 1
Be that the ratio of 1:1:1 is by soluble in water to cobaltous sulfate, nickelous sulfate, manganese sulfate according to the mol ratio of Ni, Co and Mn, the mixed solution being made into 1mol/L carries out coprecipitation reaction, the pH value controlling coprecipitation reaction is 11.2, the coprecipitation reaction product that obtains is stirred, washing, dry, obtain the Ni that D50 granularity is 3 μm 1/3co 1/3mn 1/3(OH) 2the hydroxide of nickel cobalt manganese;
The hydroxide of described nickel cobalt manganese is sintered 6h at 600 DEG C, obtains Ni 1/3co 1/3mn 1/3o 2the oxide of nickel cobalt manganese;
By the oxide of described nickel cobalt manganese and the mixing of lithium carbonate ball milling, the ratio of the molal quantity of the molal quantity that the described oxide of nickel cobalt manganese and the consumption of lithium carbonate make nickel, cobalt, manganese total and lithium is 1.1:1; The mixture obtained is warming up to 700 DEG C of insulation 4h with the speed of 3 DEG C/min, is then warming up to 1000 DEG C of insulation 12h, the product obtained is cooled naturally, obtains LiNi 1/3co 1/3mn 1/3o 2cell positive material.
Carry out scanning electron microscopy detection to the cell positive material that comparative example 1 of the present invention prepares, as shown in Figure 4, Fig. 4 is the scanning electron microscope diagram of the cell positive material that comparative example 1 of the present invention prepares to testing result.
Test compacted density and the high temperature cyclic performance of the cell positive material that comparative example 1 of the present invention prepares according to the method described above, test result is as shown in table 1.
Comparative example 2
Be that the ratio of 5:2:3 is by soluble in water to cobaltous sulfate, nickelous sulfate, manganese sulfate according to the mol ratio of Ni, Co and Mn, the mixed solution being made into 2mol/L carries out coprecipitation reaction, the pH value controlling coprecipitation reaction is 11, the coprecipitation reaction product that obtains is stirred, washing, dry, obtain the Ni that D50 granularity is 2.5 μm 0.5co 0.2mn 0.3(OH) 2the hydroxide of nickel cobalt manganese;
The hydroxide of described nickel cobalt manganese is sintered 6h at 600 DEG C, obtains Ni 0.5co 0.2mn 0.3o 2the oxide of nickel cobalt manganese;
By the oxide of described nickel cobalt manganese and the mixing of lithium carbonate ball milling, the ratio of the molal quantity of the molal quantity that the described oxide of nickel cobalt manganese and the consumption of lithium carbonate make nickel, cobalt, manganese total and lithium is 1.02:1; The mixture obtained is warming up to 700 DEG C of insulation 4h with the speed of 3 DEG C/min, is then warming up to 960 DEG C of insulation 12h, the product obtained is cooled naturally, obtains LiNi 0.5co 0.2mn 0.3o 2cell positive material.
Test compacted density and the high temperature cyclic performance of the cell positive material that comparative example 2 of the present invention prepares according to the method described above, test result is as shown in table 1.
The performance test results of the cell positive material that table 1 embodiment of the present invention and comparative example prepare
Embodiment Compacted density/gcm3 60 DEG C of 100 circulation volume conservation rates
1 3.75 96.8％
2 3.72 96.3％
3 3.78 97.2％
4 3.71 96.5％
Comparative example 1 3.50 83.1％
Comparative example 2 3.55 80.7％
As shown in Table 1, the compacted density of cell positive material that prior art provides is 3.55gcm 3, 3.50gcm 3, at 60 DEG C, after 100 circulations, capability retention is only 83.1% and 80.7%, and the compacted density of the cell positive material that the embodiment of the present invention prepares is all at 3.7gcm 3above and 60 DEG C 100 times circulation after capability retention all more than 96%; The cell positive material that the embodiment of the present invention prepares has good structural stability and can alleviate the corrosion of electrolyte to positive electrode, thus makes the lithium ion battery prepared have good cycle performance under the high temperature conditions.
As seen from the above embodiment, the invention provides a kind of cell positive material, comprise the base material of mono-crystalline structures; Be coated on the coating layer of described substrate surface, described coating layer is aluminium oxide or zirconia.Cell positive material provided by the invention comprises the base material of mono-crystalline structures, the positive electrode of this mono-crystalline structures can prevent from preparing positive plate in the process of battery and roll the Particle Breakage caused, simultaneously by the acting in conjunction of the doped chemical in cell positive material and coating layer, can improve the structural stability of positive electrode and alleviate the corrosion of electrolyte to material, lithium ion battery prepared by this positive electrode has good high temperature cyclic performance.

Claims (10)

1. a cell positive material, comprises the base material of mono-crystalline structures, and described base material is the compound shown in formula I:
LiNi xco ymn (1-x-y)y ao 2formula I;
In formula I, 0 < x < 0.6,0 < y < 1.0,0 < x+y < 1.0,0 < a < 0.1;
Y is one or more in Mg, Ti, Zr, Sr and Al;
Be coated on the coating layer of described substrate surface, described coating layer is aluminium oxide or zirconia.
2. cell positive material according to claim 1, is characterized in that, containing multiple single crystal grain in the base material of described mono-crystalline structures, the granularity of described single crystal grain is 0.5 micron ~ 5 microns.
3. cell positive material according to claim 1, is characterized in that, the granularity of the base material of described mono-crystalline structures is 3 microns ~ 8 microns.
4. cell positive material according to claim 1, is characterized in that, the thickness of described coating layer is 1 nanometer ~ 50 nanometer.
5. cell positive material according to claim 1, is characterized in that, the quality of described coating layer is 0.04% ~ 2% of described cell positive material quality.
6. a preparation method for the cell positive material in Claims 1 to 5 described in any one, comprising:
Be incubated after the oxide and lithium salts with the nickel cobalt manganese of mono-crystalline structures are carried out the first calcining, obtain intermediate product, the temperature of described first calcining is 500 DEG C ~ 800 DEG C; The oxide of described nickel cobalt manganese is the compound shown in formula II:
Ni xco ymn (1-x-y)m ao 2formula II;
Be incubated after described intermediate product is carried out the second calcining, obtain the base material of mono-crystalline structures, the temperature of described second calcining is 801 DEG C ~ 1100 DEG C;
Described base material is the compound shown in formula I:
LiNi xco ymn (1-x-y)m ao 2formula I;
In formula I and formula II, 0 < x < 0.6,0 < y < 1.0,0 < x+y < 1.0,0 < a < 0.1;
M is one or more in Mg, Ti, Zr, Sr and Al;
Carry out heat treated by after the mixing of the oxide of described base material and coated element, obtain cell positive material; Described coated element is aluminium or zirconium.
7. method according to claim 6, is characterized in that, described in there is the oxide of the nickel cobalt manganese of mono-crystalline structures preparation method be:
The mixed solution of nickel salt, manganese salt, cobalt salt and M salt is carried out coprecipitation reaction, obtain the hydroxide of nickel cobalt manganese, described M is one or more in Mg, Ti, Zr, Sr and Al, and the pH value of described coprecipitation reaction is 10 ~ 14, and the hydroxide of described nickel cobalt manganese is the compound shown in formula III:
Ni xco ymn (1-x-y)m a(OH) 2formula III;
In formula III, 0 < x < 0.6,0 < y < 1.0,0 < x+y < 1.0,0 < a < 0.1;
M is one or more in Mg, Ti, Zr, Sr and Al;
Sintered by the hydroxide of described nickel cobalt manganese, obtain the oxide of the nickel cobalt manganese of concrete mono-crystalline structures, the temperature of described sintering is 300 DEG C ~ 700 DEG C.
8. method according to claim 6, is characterized in that, the granularity of the oxide of described coated element is 5 nanometer ~ 100 nanometers.
9. method according to claim 6, is characterized in that, the temperature of described heat treated is 300 DEG C ~ 800 DEG C.
10. a lithium ion battery, the positive electrode of described lithium ion battery is the cell positive material in technique scheme Claims 1 to 5 described in any one, or the cell positive material that the method in claim 6 ~ 9 described in any one prepares.
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Cited By (20)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106505195A (en) * 2016-12-30 2017-03-15 宁波金和锂电材料有限公司 A kind of nickelic positive electrode and preparation method thereof and lithium ion battery
CN107785561A (en) * 2017-11-22 2018-03-09 江门市科恒实业股份有限公司 A kind of preparation method of high voltage monocrystalline lithium ion tertiary cathode material
CN108417790A (en) * 2018-01-30 2018-08-17 合肥国轩高科动力能源有限公司 A kind of anode material for lithium-ion batteries and its preparation method and application
CN109037619A (en) * 2018-07-06 2018-12-18 合肥国轩高科动力能源有限公司 A kind of lithium chromate cladding monocrystalline type nickel-cobalt-manganternary ternary anode material and preparation method thereof
CN109075334A (en) * 2016-03-14 2018-12-21 苹果公司 Active material of cathode for lithium ion battery
JP2019530630A (en) * 2016-09-21 2019-10-24 アップル インコーポレイテッドＡｐｐｌｅ Ｉｎｃ． Surface-stabilized cathode material for lithium ion battery and synthesis method thereof
US20200083531A1 (en) * 2018-09-11 2020-03-12 Ecopro Bm Co., Ltd. Positive electrode active material for lithium secondary battery and lithium secondary battery including the same
CN110931738A (en) * 2019-11-20 2020-03-27 广东邦普循环科技有限公司 Complex-phase high-voltage cathode material and preparation method thereof
CN111430689A (en) * 2020-03-27 2020-07-17 蜂巢能源科技有限公司 Cathode material and preparation method thereof, cathode, lithium ion battery and vehicle
CN111509205A (en) * 2020-04-21 2020-08-07 江门市科恒实业股份有限公司 Ternary cathode material for zirconium-coated lithium ion battery and preparation method thereof
CN111628157A (en) * 2020-06-30 2020-09-04 蜂巢能源科技有限公司 Cathode material, preparation method thereof and lithium ion battery
WO2021037900A1 (en) 2019-08-27 2021-03-04 Evonik Operations Gmbh Mixed lithium transition metal oxide coated with pyrogenically produced zirconium-containing oxides
WO2021037904A1 (en) 2019-08-27 2021-03-04 Evonik Operations Gmbh Mixed lithium transition metal oxide containing pyrogenically produced zirconium-containing oxides
US11114663B2 (en) 2016-09-20 2021-09-07 Apple Inc. Cathode active materials having improved particle morphologies
CN113675381A (en) * 2020-05-15 2021-11-19 深圳市比亚迪锂电池有限公司 Lithium ion battery positive electrode material, positive electrode plate and lithium ion battery
CN115072798A (en) * 2022-01-14 2022-09-20 宁夏汉尧石墨烯储能材料科技有限公司 Preparation method and application of high-compaction-density nickel cobalt lithium manganate positive electrode material
US11450846B2 (en) 2017-10-19 2022-09-20 Lg Energy Solution, Ltd. Positive electrode material for lithium secondary battery, method of preparing the same, and positive electrode for lithium secondary battery and lithium secondary battery which includes the positive electrode material
US11695108B2 (en) 2018-08-02 2023-07-04 Apple Inc. Oxide mixture and complex oxide coatings for cathode materials
US11749799B2 (en) 2018-08-17 2023-09-05 Apple Inc. Coatings for cathode active materials
US11757096B2 (en) 2019-08-21 2023-09-12 Apple Inc. Aluminum-doped lithium cobalt manganese oxide batteries

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102509784A (en) * 2011-10-17 2012-06-20 北大先行科技产业有限公司 Preparation method of lithium ion battery ternary cathode material
CN103107337A (en) * 2012-04-01 2013-05-15 湖南大学 Method for improving cycling stability of lithium ion battery anode material
CN103825015A (en) * 2014-01-10 2014-05-28 兰州金里能源科技有限公司 Preparation method of high compaction density lithium nickel cobalt manganese oxide NCM523 ternary material

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102509784A (en) * 2011-10-17 2012-06-20 北大先行科技产业有限公司 Preparation method of lithium ion battery ternary cathode material
CN103107337A (en) * 2012-04-01 2013-05-15 湖南大学 Method for improving cycling stability of lithium ion battery anode material
CN103825015A (en) * 2014-01-10 2014-05-28 兰州金里能源科技有限公司 Preparation method of high compaction density lithium nickel cobalt manganese oxide NCM523 ternary material

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* Cited by examiner, † Cited by third party
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CN114583154A (en) * 2016-03-14 2022-06-03 苹果公司 Cathode active material for lithium ion battery
US11362331B2 (en) 2016-03-14 2022-06-14 Apple Inc. Cathode active materials for lithium-ion batteries
US11114663B2 (en) 2016-09-20 2021-09-07 Apple Inc. Cathode active materials having improved particle morphologies
JP2022075768A (en) * 2016-09-21 2022-05-18 アップル インコーポレイテッド Surface stabilized cathode material for lithium ion batteries and synthesizing method for the same
JP2019530630A (en) * 2016-09-21 2019-10-24 アップル インコーポレイテッドＡｐｐｌｅ Ｉｎｃ． Surface-stabilized cathode material for lithium ion battery and synthesis method thereof
US11462736B2 (en) 2016-09-21 2022-10-04 Apple Inc. Surface stabilized cathode material for lithium ion batteries and synthesizing method of the same
CN106505195B (en) * 2016-12-30 2019-12-31 宁波容百新能源科技股份有限公司 High-nickel cathode material, preparation method thereof and lithium ion battery
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US11450846B2 (en) 2017-10-19 2022-09-20 Lg Energy Solution, Ltd. Positive electrode material for lithium secondary battery, method of preparing the same, and positive electrode for lithium secondary battery and lithium secondary battery which includes the positive electrode material
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CN109037619A (en) * 2018-07-06 2018-12-18 合肥国轩高科动力能源有限公司 A kind of lithium chromate cladding monocrystalline type nickel-cobalt-manganternary ternary anode material and preparation method thereof
US11695108B2 (en) 2018-08-02 2023-07-04 Apple Inc. Oxide mixture and complex oxide coatings for cathode materials
US11749799B2 (en) 2018-08-17 2023-09-05 Apple Inc. Coatings for cathode active materials
US20200083531A1 (en) * 2018-09-11 2020-03-12 Ecopro Bm Co., Ltd. Positive electrode active material for lithium secondary battery and lithium secondary battery including the same
US11757096B2 (en) 2019-08-21 2023-09-12 Apple Inc. Aluminum-doped lithium cobalt manganese oxide batteries
WO2021037904A1 (en) 2019-08-27 2021-03-04 Evonik Operations Gmbh Mixed lithium transition metal oxide containing pyrogenically produced zirconium-containing oxides
WO2021037900A1 (en) 2019-08-27 2021-03-04 Evonik Operations Gmbh Mixed lithium transition metal oxide coated with pyrogenically produced zirconium-containing oxides
CN110931738B (en) * 2019-11-20 2021-08-03 广东邦普循环科技有限公司 Complex-phase high-voltage cathode material and preparation method thereof
CN110931738A (en) * 2019-11-20 2020-03-27 广东邦普循环科技有限公司 Complex-phase high-voltage cathode material and preparation method thereof
CN111430689A (en) * 2020-03-27 2020-07-17 蜂巢能源科技有限公司 Cathode material and preparation method thereof, cathode, lithium ion battery and vehicle
CN111509205A (en) * 2020-04-21 2020-08-07 江门市科恒实业股份有限公司 Ternary cathode material for zirconium-coated lithium ion battery and preparation method thereof
CN113675381A (en) * 2020-05-15 2021-11-19 深圳市比亚迪锂电池有限公司 Lithium ion battery positive electrode material, positive electrode plate and lithium ion battery
CN113675381B (en) * 2020-05-15 2024-03-19 深圳市比亚迪锂电池有限公司 Lithium ion battery positive electrode material, positive electrode plate and lithium ion battery
CN111628157A (en) * 2020-06-30 2020-09-04 蜂巢能源科技有限公司 Cathode material, preparation method thereof and lithium ion battery
CN111628157B (en) * 2020-06-30 2024-03-26 蜂巢能源科技有限公司 Positive electrode material, preparation method thereof and lithium ion battery
CN115072798A (en) * 2022-01-14 2022-09-20 宁夏汉尧石墨烯储能材料科技有限公司 Preparation method and application of high-compaction-density nickel cobalt lithium manganate positive electrode material

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