CN111233052A - Nickel cobalt lithium manganate ternary positive electrode material, preparation method thereof, positive electrode and battery - Google Patents

Nickel cobalt lithium manganate ternary positive electrode material, preparation method thereof, positive electrode and battery Download PDF

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CN111233052A
CN111233052A CN202010054996.XA CN202010054996A CN111233052A CN 111233052 A CN111233052 A CN 111233052A CN 202010054996 A CN202010054996 A CN 202010054996A CN 111233052 A CN111233052 A CN 111233052A
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nickel cobalt
positive electrode
lithium manganate
nickel
electrode material
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张锐
李宝华
章立寒
冉爱华
康飞宇
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Shenzhen International Graduate School of Tsinghua University
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    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G53/00—Compounds of nickel
    • C01G53/006—Compounds containing, besides nickel, two or more other elements, with the exception of oxygen or hydrogen
    • 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
    • H01M4/50—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
    • H01M4/525—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
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
    • C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/01—Particle morphology depicted by an image
    • C01P2004/03—Particle morphology depicted by an image obtained by SEM
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
    • H01M2004/028—Positive electrodes
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Abstract

The utility model provides a nickel cobalt lithium manganate ternary positive electrode material, nickel cobalt lithium manganate ternary positive electrode material includes nickel cobalt lithium manganate granule and lithium manganate granule, wherein, the secondary particle that nickel cobalt lithium manganate granule is a plurality of primary particles and constitutes, and is adjacent form the hole between the primary particle, lithium manganate granule load in the surface and the formation of secondary particle the inner wall in hole. The application also provides a preparation method of the nickel cobalt lithium manganate ternary positive electrode material, a positive electrode comprising the nickel cobalt lithium manganate ternary positive electrode material and a battery.

Description

Nickel cobalt lithium manganate ternary positive electrode material, preparation method thereof, positive electrode and battery
Technical Field
The application relates to the field of lithium ion batteries, in particular to a nickel cobalt lithium manganate ternary positive electrode material, a preparation method thereof, a positive electrode comprising the nickel cobalt lithium manganate ternary positive electrode material and a battery comprising the positive electrode.
Background
The actual specific capacity of the lithium ion battery anode materials such as layered Lithium Cobaltate (LCO), olivine lithium iron phosphate (LFP), layered ternary materials (NCM111, NCM523 and the like) and spinel Lithium Manganate (LMO) which are commercialized in large scale at present in China is only 100-plus 170mAh/g, and the requirement of high energy density of a single battery cannot be met. In addition, although the lithium-rich layered material has very high theoretical specific capacity, the structure of the material is unstable, and irreversible lithium ion loss and crystal transformation occur in the circulating process, so that the phenomena of continuous reduction of the working voltage of the battery and poor cycle life are caused.
The high-nickel ternary material (the nickel content is more than 60 percent) has the characteristics of high energy density, moderate price, high voltage platform and the like, and is the research focus of the anode material of the lithium ion battery at present. The theoretical specific capacity of NCM811 reaches 270mAh/g, the actual specific capacity exceeding 220mAh/g can be provided, and meanwhile, the reduction of the cobalt content provides space for cost control. However, in the case of the high nickel content of the currently commercialized high nickel ternary material, the battery has the problems of reduced structural stability, insufficient rate performance, increased side reactions, and the like, which may have serious negative effects on the electrochemical characteristics and safety of the full battery.
Disclosure of Invention
In view of the above, it is necessary to provide a nickel cobalt lithium manganate ternary positive electrode material with good structural stability, high rate capability and less side reactions, so as to solve the above problems.
In addition, a preparation method of the nickel cobalt lithium manganate ternary positive electrode material is also necessarily provided.
In addition, a positive electrode of the nickel cobalt lithium manganate ternary positive electrode material is also needed to be provided.
In addition, it is also necessary to provide a battery including the positive electrode.
The utility model provides a nickel cobalt lithium manganate ternary positive electrode material, nickel cobalt lithium manganate ternary positive electrode material includes nickel cobalt lithium manganate granule and lithium manganate granule, wherein, the secondary particle that nickel cobalt lithium manganate granule is a plurality of primary particles and constitutes, and is adjacent form the hole between the primary particle, lithium manganate granule load in the surface and the formation of secondary particle the inner wall in hole.
A preparation method of a nickel cobalt lithium manganate ternary positive electrode material comprises the following steps:
providing nickel cobalt manganese hydroxide;
dispersing the nickel-cobalt-manganese hydroxide in a potassium permanganate solution to react to obtain a modified nickel-cobalt-manganese hydroxide;
drying the modified nickel-cobalt-manganese hydroxide; and
and mixing the dried modified nickel cobalt manganese hydroxide with a lithium salt, and calcining in an oxygen atmosphere to obtain the nickel cobalt lithium manganate ternary positive electrode material.
Further, the molecular formula of the nickel-cobalt-manganese hydroxide is Ni1-x-yCoxMny(OH)2Wherein, 1-x-y>0.6。
Further, the nickel-cobalt-manganese hydroxide is secondary particles formed by aggregating a plurality of primary particles, and holes are formed between adjacent primary particles.
Further, the concentration of the potassium permanganate solution is 0.1-1 mol/L.
Further, the solid content of the nickel-cobalt-manganese hydroxide in the potassium permanganate solution is 10% -80%.
Further, the molar ratio of the modified nickel cobalt manganese hydroxide to the lithium salt is (1.04: 1) - (1.12: 1).
Further, the lithium salt includes at least one of lithium hydroxide, lithium carbonate, and lithium acetate.
A positive electrode comprises the nickel cobalt lithium manganate ternary positive electrode material.
A battery comprising the positive electrode.
The nickel cobalt lithium manganate ternary positive electrode material comprises a plurality of holes, wherein the holes provide transmission channels for lithium ions, and the rate capability of a battery is enhanced; in addition, the lithium manganate particles with stable structures are loaded on the surfaces of the primary particles, so that the contact between the nickel cobalt lithium manganate particles in the nickel cobalt lithium manganate ternary positive electrode material and an electrolyte can be reduced, and side reactions are increased; the holes provide relaxation space for volume change of the nickel cobalt lithium manganate ternary positive electrode material in the charging and discharging process, and cracks of the nickel cobalt lithium manganate ternary positive electrode material after charging and discharging circulation are relieved, so that the cycle life of the battery is prolonged.
Drawings
Fig. 1 is a flowchart of a preparation method of a nickel cobalt lithium manganate ternary positive electrode material provided in an embodiment of the present application.
Fig. 2 is an X-ray diffraction pattern of the nickel cobalt lithium manganate ternary positive electrode materials prepared in example 1 and comparative example 1.
Fig. 3A is a scanning electron microscope test chart of the nickel cobalt lithium manganate ternary cathode material prepared in example 3.
Fig. 3B is a scanning electron microscope test chart of the nickel cobalt lithium manganate ternary cathode material prepared in comparative example 3.
Fig. 4 is a scanning electron microscope test chart of the internal structure of the nickel cobalt lithium manganate ternary positive electrode material prepared in example 3.
Fig. 5A is a rate performance test chart of the assembled battery of example 2.
Fig. 5B is a rate performance test chart of the assembled battery of comparative example 2.
The following detailed description will further illustrate the present application in conjunction with the above-described figures.
Detailed Description
In order that the above objects, features and advantages of the present application can be more clearly understood, a detailed description of the present application will be given below with reference to the accompanying drawings and detailed description. In addition, the embodiments and features of the embodiments of the present application may be combined with each other without conflict. In the following description, numerous specific details are set forth to provide a thorough understanding of the present application, and the described embodiments are merely a subset of the embodiments of the present application, rather than all embodiments. All other embodiments obtained by a person of ordinary skill in the art without any inventive work based on the embodiments in the present application are within the scope of protection of the present application.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this application belongs. The terminology used herein in the description of the present application is for the purpose of describing particular embodiments only and is not intended to be limiting of the application. As used herein, the term "and/or" includes all and any combination of one or more of the associated listed items.
In various embodiments of the present application, for convenience in description and not limitation, the term "coupled" as used in the specification and claims of the present application is not limited to physical or mechanical connections, either direct or indirect. "upper", "lower", "above", "below", "left", "right", and the like are used merely to indicate relative positional relationships, and when the absolute position of the object being described is changed, the relative positional relationships are changed accordingly.
Referring to fig. 1, an embodiment of the present application provides a method for preparing a nickel cobalt lithium manganate ternary positive electrode material, including the following steps:
step S1: nickel cobalt manganese hydroxides are provided.
The molecular formula of the nickel-cobalt-manganese hydroxide is Ni1-x-yCoxMny(OH)2，1-x-y>0.6。
The nickel-cobalt-manganese hydroxide is spherical particles, and the spherical nickel-cobalt-manganese hydroxide is secondary particles (i.e., large particles) formed by aggregating a plurality of primary particles (i.e., small particles), and it can be understood that pores are formed between adjacent primary particles.
Step S2: dispersing the nickel-cobalt-manganese hydroxide in a potassium permanganate solution for reaction to obtain a modified nickel-cobalt-manganese hydroxide, and drying the modified nickel-cobalt-manganese hydroxide.
The concentration of the potassium permanganate solution is 0.1-1 mol/L.
The solid content of the nickel-cobalt-manganese hydroxide in the potassium permanganate solution is 10% -80%, namely the mass of the nickel-cobalt-manganese hydroxide is 10g-80g, and the nickel-cobalt-manganese hydroxide is dispersed in 100g of water.
Specifically, preparing an aqueous solution of potassium permanganate with a certain concentration; and then dispersing the nickel-cobalt-manganese hydroxide in the potassium permanganate solution in a manner including but not limited to mechanical stirring and ultrasonic dispersion, wherein the rotation speed of the mechanical stirring is 50r/min-200r/min, the stirring is carried out for 0.5h-2h, and the time of the ultrasonic dispersion is 30min-100 min. In the process, potassium permanganate and nickel-cobalt-manganese hydroxide are subjected to chemical reaction, on one hand, potassium permanganate has an etching effect on the nickel-cobalt-manganese hydroxide, the potassium permanganate has an etching effect at the place where the potassium permanganate solution is contacted with the nickel-cobalt-manganese strong oxide, for example, the potassium permanganate solution enters holes of the nickel-cobalt-manganese hydroxide, and the potassium permanganate reacts with the nickel-cobalt-manganese hydroxide in the holes of the nickel-cobalt-manganese hydroxide to further increase the volume of the holes; on the other hand, the potassium permanganate itself decomposes to produce manganese dioxide, which is loaded on the surface of the nickel cobalt manganese hydroxide, wherein the surface includes the outer surface of the nickel cobalt manganese hydroxide and the surface forming the inner wall of the hole.
And finally, filtering and washing with water to obtain the nickel-cobalt-manganese hydroxide which forms holes and is loaded with manganese dioxide, namely the modified nickel-cobalt-manganese hydroxide. The modified nickel-cobalt-manganese hydroxide is nickel-cobalt-manganese hydroxide with the surface coated with manganese dioxide.
Step S3: and mixing the dried modified nickel cobalt manganese hydroxide with lithium salt, and calcining in an oxygen atmosphere to obtain the nickel cobalt lithium manganate ternary positive electrode material.
The molar ratio of the modified nickel cobalt manganese hydroxide to the lithium salt is (1.04: 1) - (1.12: 1).
The lithium salt includes at least one of lithium hydroxide, lithium carbonate, and lithium acetate.
The calcining atmosphere is pure oxygen atmosphere, and the calcining step comprises the following steps: firstly, heating to 450-500 ℃ at a heating rate of 4-15 ℃/min, and preserving heat for 2-6 h; then heating to 700-850 ℃, and preserving heat for 6-24 h; and finally, naturally cooling to room temperature. Wherein, in the calcination process, nickel cobalt manganese hydroxide and lithium salt reaction generate nickel cobalt lithium manganate ternary positive electrode material, manganese dioxide is changed into lithium manganate granule load nickel cobalt lithium manganate ternary positive electrode material, lithium manganate granule load in nickel cobalt lithium manganate ternary positive electrode material's surface, wherein, the surface includes nickel cobalt lithium manganate ternary positive electrode material's surface and formation the surface of the inner wall of hole.
The application still provides a nickel cobalt lithium manganate ternary positive electrode material, nickel cobalt lithium manganate ternary positive electrode material includes nickel cobalt lithium manganate granule and lithium manganate granule, wherein, the secondary particle that nickel cobalt lithium manganate granule constitutes for a plurality of primary particles, and is adjacent form the hole between the primary particle, lithium manganate granule load in the surface and the formation of secondary particle the inner wall of hole.
The invention also provides a positive electrode, which comprises a current collector and a coating material arranged on the surface of the current collector, wherein the coating material comprises the nickel cobalt lithium manganate ternary positive electrode material, a conductive material and a binder, the nickel cobalt lithium manganate ternary positive electrode material, the conductive material and the binder are dispersed in a solvent according to a certain proportion, and are uniformly mixed to obtain a dispersion solution, and then the dispersion solution is coated on the current collector, dried and sliced to obtain the positive electrode.
The present invention also provides a battery including the positive electrode, the negative electrode, a separator disposed between the positive electrode and the negative electrode, and an electrolyte.
The present application will be described below with reference to specific examples.
Example 1
Preparing a positive electrode material: 20g of nickel cobalt manganese hydroxide (Ni)0.70Co0.15Mn0.15(OH)2) The particle size D50 of the nickel-cobalt-manganese hydroxide is 16 mu m, and the tap density is 2.1g/cm3。
Dispersing the nickel-cobalt-manganese hydroxide in 100mL of potassium permanganate solution with the concentration of 0.2mol/L, magnetically stirring for 1 hour at the rotating speed of 200r/min, collecting, washing and drying the nickel-cobalt-manganese hydroxide treated by the potassium permanganate solution by adopting a suction filtration method to obtain the modified nickel-cobalt-manganese hydroxide.
Mixing the modified nickel cobalt manganese hydroxide with lithium hydroxide monohydrate (LiOH. H)2O) is mixed for 0.5h by a ball mill according to the mol ratio of 1:1.06, then the mixture is calcined in the oxygen atmosphere, the temperature is raised to 500 ℃ at the temperature rise rate of 5 ℃/min, and the temperature is preserved for 4 h; then heating to 800 ℃ at the same heating rate, and preserving heat for 10 h; naturally cooling to room temperature; and collecting the sintered product, and grading, sieving and demagnetizing to obtain the nickel cobalt lithium manganate ternary positive electrode material.
Preparing a positive pole piece: the nickel cobalt lithium manganate ternary positive electrode materials prepared in examples 1 to 3 and comparative examples 1 to 3 are respectively used as active materials, and are mixed with acetylene black and PVDF according to the mass ratio of 8: 1:1, mixing, adding NMP as a solvent to prepare slurry; coating the slurry on an aluminum foil current collector, vacuum drying to remove the solvent, rolling and cutting to obtain a positive pole piece with the diameter of 10 mm; and drying the positive pole piece again at 120 ℃ in vacuum for 12 h. Wherein the compacted density of the positive pole piece is 3.2g/cm3。
Preparing a battery: a metal lithium sheet with the diameter of 8mm is taken as a negative pole piece, the thickness of a diaphragm is 25 mu m, and the electrolyte is 1mol/L LiPF6In EC: EMC: DEC ═ 1: 1:1, in a clear solution. And sequentially stacking the positive pole piece, the diaphragm and the negative pole piece in an argon atmosphere to assemble the button cell, wherein the content of the electrolyte is 75 mu L.
Example 2
The difference from example 1 is: the molecular formula of the nickel-cobalt-manganese hydroxide is Ni0.8Co0.1Mn0.1(OH)2The mass of the nickel-cobalt-manganese hydroxide is 30g, the particle size D50 of the nickel-cobalt-manganese hydroxide is 10.4 mu m, and the tap density is2.0g/cm3。
The modified nickel cobalt manganese hydroxide is mixed with lithium carbonate (Li)2CO3) The molar ratio of the raw materials is 1: 1.05. The calcining step is as follows: heating to 480 ℃ at the heating rate of 10 ℃/min, and keeping the temperature for 4 h; then raising the temperature to 780 ℃ at the same temperature raising rate, preserving the temperature for 12h, and naturally cooling to room temperature.
The compacted density of the positive pole piece is 3.1g/cm3。
The rest is the same as embodiment 1, and is not described herein again.
Example 3
The difference from example 1 is: the molecular formula of the nickel-cobalt-manganese hydroxide is Ni0.85Co0.10Mn0.05(OH)2The mass of the nickel-cobalt-manganese hydroxide is 30g, the particle size D50 of the nickel-cobalt-manganese hydroxide is 9.2 mu m, and the tap density is 2.0g/cm3。
The modified nickel-cobalt-manganese hydroxide and lithium acetate (CH)3COOLi) in a molar ratio of 1: 1.05. The calcining step is as follows: heating to 450 ℃ at the heating rate of 10 ℃/min, and keeping the temperature for 5 hours; then the temperature is raised to 740 ℃ at the same heating rate, the temperature is kept for 6h, and the temperature is naturally cooled to the room temperature.
The compacted density of the positive pole piece is 3.0g/cm3。
The rest is the same as embodiment 1, and is not described herein again.
Comparative example 1
The difference from example 1 is: the nickel cobalt manganese hydroxide (Ni)0.70Co0.15Mn0.15(OH)2) Without treatment with potassium permanganate solution, i.e. the nickel cobalt manganese hydroxide is directly reacted with lithium hydroxide monohydrate (LiOH. H)2O) mixing and calcining.
The compacted density of the positive pole piece is 3.5g/cm3。
The rest is the same as embodiment 1, and is not described herein again.
Comparative example 2
The difference from example 2 is: the nickel cobalt manganese hydroxide (Ni)0.8Co0.1Mn0.1(OH)2) Without passing through potassium permanganate solutionTreatment, i.e. direct reaction of the nickel cobalt manganese hydroxide with lithium carbonate (Li)2CO3) Mixing and calcining.
The rest is the same as embodiment 2, and is not described herein again.
Comparative example 3
The difference from example 3 is: the nickel cobalt manganese hydroxide (Ni)0.85Co0.10Mn0.05(OH)2) The nickel-cobalt-manganese hydroxide is directly mixed with lithium acetate (CH) without being treated by potassium permanganate solution3COOLi) and calcining.
The compacted density of the positive pole piece is 3.4g/cm3。
The rest is the same as embodiment 3, and is not described herein.
Please refer to table 1, which shows some conditions for preparing the lithium nickel cobalt manganese oxide ternary cathode material of examples 1-3 and comparative examples 1-3.
TABLE 1
Figure BDA0002372499480000091
Referring to fig. 2, X-ray diffraction tests are performed on the nickel cobalt lithium manganate ternary positive electrode materials prepared in example 1 and comparative example 1, and it can be seen from the test results that: and an X-ray diffraction test chart does not have an impurity peak, and the nickel cobalt lithium manganate ternary positive electrode material is nickel cobalt lithium manganate particles. In addition, since the amount of lithium manganate contained in the nickel cobalt lithium manganate ternary positive electrode material prepared in example 1 is very small, no obvious characteristic peak appears in an X-ray diffraction test chart.
Scanning electron microscope tests are respectively carried out on the nickel cobalt lithium manganate ternary positive electrode materials prepared in example 3 and comparative example 3, and the test results are shown in fig. 3A and fig. 3B, wherein fig. 3A is the test result of example 3, and fig. 3B is the test result of comparative example. As is apparent from fig. 3A and 3B, the lithium nickel cobalt manganese oxide ternary positive electrode materials prepared in example 3 and comparative example 3 are secondary particles composed of primary particles, and pores are formed on the surface of the lithium nickel cobalt manganese oxide ternary positive electrode material, however, the pores in example 3 are very obvious compared with comparative example 3, and the primary particles in comparative example 3 are tightly connected to hinder the transmission of lithium ions. Referring to fig. 4, fig. 4 is a scanning electron microscope test chart of the internal structure of the lithium nickel cobalt manganese oxide ternary positive electrode material prepared in example 3, wherein the holes are obvious, and the primary particles are approximately radially arranged from the center to the outside to provide a transmission channel for lithium ions and enhance the rate capability of the battery; in addition, the lithium manganate particles with stable structures are loaded on the surfaces of the primary particles, so that the contact between the nickel cobalt lithium manganate particles in the nickel cobalt lithium manganate ternary positive electrode material and an electrolyte can be reduced, and side reactions are increased; the holes provide relaxation space for volume change of the nickel cobalt lithium manganate ternary positive electrode material in the charging and discharging process, and cracks of the nickel cobalt lithium manganate ternary positive electrode material after charging and discharging circulation are relieved, so that the cycle life of the battery is prolonged.
The nickel cobalt lithium manganate ternary positive electrode materials prepared in examples 1 to 3 and comparative examples 1 to 3 were respectively tested for particle size D50, specific surface area, and tap density pole piece compaction density, and the test results are shown in table 2.
TABLE 2
Figure BDA0002372499480000101
Figure BDA0002372499480000111
Standing the assembled button cell for 12 hours to enable the electrolyte to be fully soaked on the surface of the electrode and the open-circuit voltage to be stable; performing constant current charging on the button cell at a current density of 0.1C, wherein the cut-off voltage is 4.3V, performing constant voltage charging for 0.5 hour at a voltage of 4.3V, and performing constant current discharging at a current density of 0.1C, wherein the discharging voltage is 3.0V; and carrying out the second cycle in the same charging and discharging process to complete the activation of the battery.
The batteries in examples 1 to 3 and comparative examples 1 to 3, in which activation was completed, were subjected to charge and discharge cycle performance tests at current densities of 0.2C and 5C. The specific capacity of the initial discharge is shown in table 3.
TABLE 3
Figure BDA0002372499480000112
The test results of example 1 and comparative example 1, example 2 and comparative example 2, and example 3 and comparative example 3 are respectively compared, and it can be known that the first discharge specific capacity of the battery assembled by the nickel cobalt lithium manganate ternary cathode material prepared after the potassium permanganate modification is higher than that of the cathode material which is not modified.
Referring to fig. 5A and 5B, fig. 5A and 5B are graphs showing rate performance tests of the assembled batteries of example 2 and comparative example 2, wherein the battery of example 2 has a specific discharge capacity up to 198mAhg after cycling at a large rate and a charge-discharge capacity rising again under the same current density test, and the battery of example 2 has a specific discharge capacity up to 198mAhg after cycling at a large rate and performing charge-discharge cycling at a small current-1Comparative example 2, however, had a specific discharge capacity of 190mAhg-1The lithium nickel cobalt manganese oxide ternary positive electrode material prepared in example 2 can still maintain higher charge-discharge specific capacity after being charged and discharged at a high rate.
The nickel cobalt lithium manganate ternary positive electrode material comprises a plurality of holes, wherein the holes provide transmission channels for lithium ions, and the rate capability of a battery is enhanced; in addition, the lithium manganate particles with stable structures are loaded on the surfaces of the primary particles, so that the contact between the nickel cobalt lithium manganate particles in the nickel cobalt lithium manganate ternary positive electrode material and an electrolyte can be reduced, and side reactions are increased; the holes provide relaxation space for volume change of the nickel cobalt lithium manganate ternary positive electrode material in the charging and discharging process, and cracks of the nickel cobalt lithium manganate ternary positive electrode material after charging and discharging circulation are relieved, so that the cycle life of the battery is prolonged.
Although the present application has been described in detail with reference to the preferred embodiments, it will be understood by those skilled in the art that various changes may be made and equivalents may be substituted without departing from the spirit and scope of the present application.

Claims (10)

1. The utility model provides a nickel cobalt lithium manganate ternary positive electrode material, its characterized in that, nickel cobalt lithium manganate ternary positive electrode material includes nickel cobalt lithium manganate granule and lithium manganate granule, wherein, the secondary particle that nickel cobalt lithium manganate granule constitutes for a plurality of primary particles, and is adjacent form the hole between the primary particle, lithium manganate granule load in the surface of secondary particle and formation the inner wall in hole.
2. The preparation method of the nickel cobalt lithium manganate ternary cathode material is characterized by comprising the following steps of:
providing nickel cobalt manganese hydroxide;
dispersing the nickel-cobalt-manganese hydroxide in a potassium permanganate solution to react to obtain a modified nickel-cobalt-manganese hydroxide;
drying the modified nickel-cobalt-manganese hydroxide; and
and mixing the dried modified nickel cobalt manganese hydroxide with a lithium salt, and calcining in an oxygen atmosphere to obtain the nickel cobalt lithium manganate ternary positive electrode material.
3. The method for preparing the nickel cobalt manganese acid lithium ternary positive electrode material as claimed in claim 2, wherein the molecular formula of the nickel cobalt manganese hydroxide is Ni1-x-yCoxMny(OH)2Wherein, 1-x-y>0.6。
4. The method for preparing the nickel cobalt manganese acid lithium ternary positive electrode material of claim 3, wherein the nickel cobalt manganese hydroxide is a secondary particle formed by agglomerating a plurality of primary particles, and pores are formed between adjacent primary particles.
5. The method for preparing the nickel cobalt lithium manganate ternary positive electrode material of claim 2, wherein the concentration of the potassium permanganate solution is 0.1mol/L-1 mol/L.
6. The method for preparing the nickel cobalt manganese acid lithium ternary positive electrode material according to claim 2, wherein the solid content of the nickel cobalt manganese hydroxide in the potassium permanganate solution is 10% -80%.
7. The method for preparing the nickel cobalt lithium manganate ternary cathode material of claim 2, wherein the molar ratio of the modified nickel cobalt manganese hydroxide to the lithium salt is (1.04: 1) - (1.12: 1).
8. The method for preparing the nickel cobalt lithium manganate ternary positive electrode material of claim 2, wherein said lithium salt comprises at least one of lithium hydroxide, lithium carbonate and lithium acetate.
9. A positive electrode comprising the nickel cobalt lithium manganate ternary positive electrode material of claim 1.
10. A battery comprising the positive electrode of claim 9.
CN202010054996.XA 2020-01-17 2020-01-17 Nickel cobalt lithium manganate ternary positive electrode material, preparation method thereof, positive electrode and battery Pending CN111233052A (en)

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