CN113903907B - Preparation method of tungsten-coated and doped monocrystal nickel-rich ternary cathode material - Google Patents

Preparation method of tungsten-coated and doped monocrystal nickel-rich ternary cathode material Download PDF

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CN113903907B
CN113903907B CN202111175709.1A CN202111175709A CN113903907B CN 113903907 B CN113903907 B CN 113903907B CN 202111175709 A CN202111175709 A CN 202111175709A CN 113903907 B CN113903907 B CN 113903907B
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nickel
lithium
tungsten
rich
monocrystal
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CN113903907A (en
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周文政
区丽敏
农盛恒
黄甜甜
黄海富
梁先庆
刘海镇
蓝志强
黄丹
郭进
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Guangxi University
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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
    • H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
    • H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—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
    • H01M4/62—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 discloses a preparation method of a tungsten-coated and doped monocrystal nickel-rich ternary cathode material, which specifically comprises the following steps: (1) Mixing the nickel-cobalt-manganese ternary precursor with a lithium source, calcining, and ball milling to obtain a monocrystal nickel-rich ternary positive electrode material; (2) And mixing the monocrystal nickel-rich ternary anode material with a tungsten source, calcining, and cooling to obtain the monocrystal nickel-rich ternary anode material coated and doped with tungsten. According to the invention, the independent coating, independent doping and arbitrary regulation of both coating and doping of the monocrystal nickel-rich ternary positive electrode material are realized by regulating and controlling the dosage of the tungsten source, so that the structural stability of the monocrystal nickel-rich ternary positive electrode material is effectively enhanced, the polarization of the material is reduced, and the diffusion kinetics of lithium ions is improved, thereby simultaneously improving the cycle stability and the multiplying power performance of the battery.

Description

Preparation method of tungsten-coated and doped monocrystal nickel-rich ternary cathode material
Technical Field
The invention relates to the technical field of lithium ion battery anode materials, in particular to a preparation method of a tungsten-coated and doped monocrystal nickel-rich ternary anode material.
Background
The lithium ion battery has the advantages of small self-discharge, no memory effect, high output voltage, long cycle life, environmental protection and the like, and has wide development prospect in the field of new energy automobiles. At present, along with the rapid development of new energy automobiles, more and more electric automobiles start to enter the life of common consumers, so that the demands of people on the endurance mileage and the service life of the electric automobiles are continuously improved. Therefore, it is important to develop lithium ion batteries with higher energy density and cycle life.
The positive electrode material is an important part of the lithium ion battery, and the performance of the positive electrode material is critical to the performance of the lithium ion battery, such as the capacity of the positive electrode material determines the upper limit of the capacity of the whole battery, and the like. Currently, the positive electrode materials in the market mainly comprise lithium cobaltate, lithium manganate, nickel cobalt manganese ternary system and lithium iron phosphate. The above-mentioned conventional positive electrode materials have respective problems with respect to the nickel-cobalt-manganese ternary system. Such as: cobalt in lithium cobaltate is expensive and has high cost; the lithium manganate has an unstable structure in the discharging process, is greatly influenced by temperature, and is easy to cause the deterioration of battery performance; the lithium iron phosphate has low conductivity, small lithium ion diffusion coefficient and poor high-temperature performance. Moreover, these lithium transition metal oxides generally have insufficient energy density, and it is difficult to make a breakthrough in battery energy density by modifying the composition and structure.
The ternary positive electrode material has the advantages of high specific capacity, long cycle life and the like, so that the ternary positive electrode material becomes a hot material for the positive electrode of the lithium ion battery, and a plurality of problems still need to be solved. For example, a large number of grain boundaries exist in secondary particles of the polycrystalline ternary cathode material, and in the charging and discharging process of a battery, the polycrystalline ternary cathode material is easy to crack due to anisotropic lattice change, so that microcracks are generated in the secondary particles, and the cycle performance and the thermal stability of the material are reduced. In addition, the surface residual alkali can aggravate side reactions occurring between the active material and the electrolyte in the reaction process, and release gas, thereby affecting the life and safety performance of the battery.
Compared with the polycrystalline ternary positive electrode material, the single crystal ternary positive electrode material system only keeps primary particles, has no grain boundary in the intrinsic structure, effectively relieves the formation of micro/nano cracks, has better structural integrity, and has better cycle stability and thermal stability than the polycrystalline ternary positive electrode material, thus receiving extensive research and attention. However, the intrinsic performance enhancement of single crystals relative to polycrystalline ternary cathode materials is also relatively limited. In addition, the primary particle size of the monocrystal ternary cathode material is relatively large, and the ion diffusion path is long, so that the multiplying power performance of the monocrystal ternary cathode material is poor, and the monocrystal ternary cathode material is limited in application to high-power electric vehicle types. Therefore, the development process of the technical scheme is simple, the structural stability and the conductivity of the monocrystal ternary cathode material are further improved through doping, cladding and the like, and the monocrystal ternary cathode material has important scientific significance.
At present, the modification method of the ternary positive electrode material mainly comprises two methods of coating and doping. The surface coating is mainly used as a protective layer for isolating the electrolyte from direct contact with the active electrode material, so that a series of side reactions, such as reduction of precipitation of transition metals, formation of thinner CEI films, reduction of precipitation of oxygen atoms and the like, are greatly reduced, and the electrochemical stability is improved. And the protective layer can relieve structural collapse of the active material caused by volume change generated by lithium removal/lithium intercalation in the charge and discharge process. The doping modification can reduce cation mixing, improve the stability of the layered structure, widen the diffusion channel of lithium ions and improve the conductivity of the material.
In the existing technical method for modifying the tungsten source of the nickel-rich ternary cathode material, the modification object is a polycrystalline material. In addition, the preparation method only realizes one of single cladding, single doping and cladding and doping, and does not change parameter details and realize full coverage of three conditions.
Therefore, the coating and doping are coordinated and coordinated through reasonable design, so that the modified monocrystal nickel-rich ternary positive electrode material is an important exploration direction for modification of the monocrystal nickel-rich ternary positive electrode material at present and in the future.
Disclosure of Invention
In view of the above, the present invention aims to provide a method for preparing a tungsten coated and doped monocrystal nickel-rich ternary positive electrode material, which solves the defects in the prior art.
In order to achieve the above purpose, the present invention adopts the following technical scheme:
a preparation method of a tungsten coated and doped monocrystal nickel-rich ternary cathode material aims at the monocrystal nickel-rich ternary cathode material, and a single coating, single doping and a coating and doping modification method of the material are simultaneously realized in one preparation method, and specifically comprises the following steps:
(1) Mixing the nickel-cobalt-manganese ternary precursor with a lithium source, calcining, and ball milling to obtain a monocrystal nickel-rich ternary positive electrode material;
(2) And mixing the monocrystal nickel-rich ternary anode material with a tungsten source, calcining, and cooling to obtain the monocrystal nickel-rich ternary anode material coated and doped with tungsten.
The preparation method has the beneficial effects that single coating, single doping and both coating and doping of the monocrystal nickel-rich ternary positive electrode material are simultaneously realized in only one preparation method, so that the rate capability and the cycle performance of the monocrystal material are effectively improved. In addition, the preparation method of the invention has the advantages of short preparation time, simple operation process, low cost of the selected raw materials, easy obtainment and better performance of the obtained materials than the comparison sample.
Further, in the step (1), the chemical formula of the nickel-cobalt-manganese ternary precursor is Ni 0.6 Co 0.2 Mn 0.2 (OH) 2 。
The technical scheme has the beneficial effects that the ternary nickel-cobalt-manganese precursor can determine a specific ternary duty ratio for the monocrystal nickel-rich ternary positive electrode material.
Further, in the step (1), the lithium source is at least one of lithium hydroxide, lithium carbonate, lithium oxide, lithium chloride, lithium nitrate and lithium oxalate.
The technical scheme has the advantages that a lithium source selection scheme is provided for preparing the ternary positive electrode material, and the lithium source selection scheme is implemented and optimized.
Further, in the step (1), the molar ratio of Li in the lithium source to Ni+Co+Mn in the ternary precursor of nickel, cobalt and manganese is 1 (1.0-1.1).
The adoption of the further technical scheme has the advantages that the excessive lithium can compensate the loss of lithium in the calcination process, the proper excessive lithium can improve the crystallization degree of the material, the mixed discharge of lithium and nickel is reduced, and the ternary anode material with a better layered structure is obtained; however, too high lithium doping amount can increase particle size and surface roughness, reduce the intercalation and deintercalation rate of lithium ions, reduce the conductivity of the positive electrode material and further reduce the multiplying power capacity; and the excessive lithium doping amount can lead residual alkali to react with electrolyte to release gas, so that the safety and the cycle life of the battery are affected.
Further, in the step (1), the temperature rising rate of calcination is 2-6 ℃/min, the temperature is 500-1000 ℃, the calcination atmosphere is air and/or oxygen, and the time is 3-15h.
The adoption of the further technical scheme has the beneficial effect of providing preferable preparation process conditions for the factors such as the temperature rising rate, the heat preservation temperature, the atmosphere, the heat preservation time and the like involved in the stage.
Further, in the step (1), the ball-milling ball-material ratio is 10:1, the rotating speed is 200-500r/min, and the time is 0.5-2h.
The technical scheme has the beneficial effects that the ball milling conditions are optimized so that the secondary particles of the ternary positive electrode material can be effectively dispersed, and the ideal monocrystal ternary positive electrode material is obtained.
Further, in the step (1), the chemical formula of the single crystal nickel-rich ternary positive electrode material is: li (Li) a Ni x Co y Mn 1-x-y O 2 The method comprises the steps of carrying out a first treatment on the surface of the Wherein x is more than or equal to 0.6 and less than or equal to 1, y is more than or equal to 0.20, z is more than or equal to 0 and less than or equal to 0.20, and x+y+z=1; a is more than or equal to 0.95 and less than or equal to 1.10.
The adoption of the further technical scheme has the beneficial effects that the obtained monocrystal nickel-rich ternary positive electrode material with the element in the ratio range has the advantages of more excellent structural stability, circulation stability, thermal stability and the like.
Further, in the step (2), the tungsten source is at least one of tungsten trioxide, lithium tungstate, sodium tungstate and tungstic acid.
The adoption of the further technical scheme has the advantages that the optimized tungsten source selected by the invention can stabilize the crystal structure of the anode material, effectively inhibit side reaction and improve the electrochemical performance of the anode material.
Further, in the step (2), the mass of the tungsten source is 0.01% -3% of the mass of the mixture of the monocrystal nickel-rich ternary cathode material and the tungsten source.
The adoption of the further technical scheme has the beneficial effects that the single doping, single cladding or both doping and cladding of the monocrystal nickel-rich ternary anode material are realized by regulating and controlling the quantity of the tungsten source.
In the step (2), the temperature rising rate of calcination is 2-6 ℃/min, the temperature is 400-900 ℃, the calcination atmosphere is argon, and the time is 1-5h.
The adoption of the further technical scheme has the beneficial effects that the two-step calcination process condition is optimized to enable the tungsten source to successfully modify the positive electrode material, so that the tungsten-coated and doped monocrystal nickel-rich ternary positive electrode material is obtained.
Compared with the prior art, the invention has the following beneficial effects:
1. compared with the traditional method for improving the circulation stability of the material by coating, doping or synergistic modification of the polycrystalline ternary cathode material, the method provided by the invention has the advantages that the modification of the monocrystal nickel-rich ternary cathode material is realized by regulating and controlling the dosage of the tungsten source, the structural stability of the monocrystal nickel-rich ternary cathode material is effectively enhanced, the polarization of the material is reduced, and the diffusion kinetics of lithium ions is improved, so that the circulation stability and the multiplying power performance of the battery are improved.
2. According to the preparation method, through a simple two-step calcination method, in the same preparation method, by effectively regulating and controlling the quantity of a tungsten source, not only can the single tungsten doping and the single tungsten cladding of the single crystal nickel-rich ternary cathode material be realized, but also the cladding and the doping of the single crystal nickel-rich ternary cathode material can be realized, and the preparation method is a key innovation of the preparation method, and has important significance for the development of ternary cathode materials, in particular to the modification means of the single crystal nickel-rich ternary cathode material.
3. The preparation method of the tungsten-coated and doped monocrystal nickel-rich ternary anode material is simple to operate, the required material can be obtained by only two-step calcination, and the process is environment-friendly and suitable for large-scale production.
Drawings
FIG. 1 is an XRD contrast pattern of samples prepared in examples 1-3 and comparative examples;
FIG. 2 is a scanning electron microscope image of a sample prepared in comparative example 1;
FIG. 3 is a scanning electron microscope image of the sample prepared in example 2;
FIG. 4 is a chart showing the Fourier transform of the HRTEM image and selected areas of the sample prepared in comparative example 1;
FIG. 5 is a chart of the HRTEM image and the Fourier transform image (coating) of selected areas of the sample prepared in example 1;
FIG. 6 is a chart of the HRTEM of the sample prepared in example 2 and the Fourier transform of selected areas (coating doped lithium-rich layer);
FIG. 7 is a chart of the HRTEM image and the Fourier transform image (doping) of selected areas of the sample prepared in example 3;
FIG. 8 is a graph showing the cycle performance of the samples prepared in examples 1-3 and comparative example 1 (corresponding capacity curves at 300 turns are example 2, example 1, example 3 and comparative example 1 in order from top to bottom);
FIG. 9 is a graph showing the rate performance of the samples prepared in examples 1-3 and comparative example 1.
Detailed Description
The following description of the embodiments of the present invention will be made clearly and completely, and it is apparent that the described embodiments are only some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Example 1
The preparation method of the tungsten coated and/or doped monocrystal nickel-rich ternary positive electrode material aims at the monocrystal nickel-rich ternary positive electrode material, and only one preparation method is used for simultaneously realizing single coating, single doping and both coating and doping modification of the material, and specifically comprises the following steps:
(1) 4.7038g of Ni, co and Mn ternary precursor Ni 0.6 Co 0.2 Mn 0.2 (OH) 2 Mixing with 2.2692g lithium hydroxide, placing into a calciner, heating to 950 deg.C at a heating rate of 5 deg.C/min under oxygen atmosphere, calcining for 10 hr, and placing into balls according to a ball-to-material ratio of 10:1Ball milling for 1h in a mill at a rotating speed of 200r/min to obtain the monocrystal nickel-rich ternary cathode material LiNi 0.6 Co 0.2 Mn 0.2 O 2 ；
Wherein, li and Ni-Co-Mn ternary precursor Ni in lithium hydroxide 0.6 Co 0.2 Mn 0.2 (OH) 2 The molar ratio of Ni to Co to Mn is 1:1.06;
(2) Monocrystal nickel-enriched ternary anode material LiNi 0.6 Co 0.2 Mn 0.2 O 2 Mixing with tungsten trioxide, then placing into a calciner, heating to 800 ℃ at a heating rate of 5 ℃/min under argon atmosphere, calcining for 2 hours, and cooling along with the calciner to obtain the tungsten-coated and doped monocrystal nickel-rich ternary anode material;
wherein the tungsten trioxide has the mass of monocrystal nickel-rich ternary anode material LiNi 0.6 Co 0.2 Mn 0.2 O 2 0.5% of the mass of the mixture with tungsten trioxide.
Example 2
The preparation method of the tungsten coated and/or doped monocrystal nickel-rich ternary positive electrode material aims at the monocrystal nickel-rich ternary positive electrode material, and only one preparation method is used for simultaneously realizing single coating, single doping and both coating and doping modification of the material, and specifically comprises the following steps:
(1) 4.7038g of Ni, co and Mn ternary precursor Ni 0.6 Co 0.2 Mn 0.2 (OH) 2 Mixing with 2.2692g of lithium hydroxide, then placing into a calciner, heating to 950 ℃ at a heating rate of 5 ℃/min under an oxygen atmosphere, calcining for 10 hours, and then placing into a ball mill according to a ball-material ratio of 10:1, ball-milling for 1 hour at a rotating speed of 200r/min to obtain the monocrystal nickel-rich ternary anode material LiNi 0.6 Co 0.2 Mn 0.2 O 2 ；
Wherein, li and Ni-Co-Mn ternary precursor Ni in lithium hydroxide 0.6 Co 0.2 Mn 0.2 (OH) 2 The molar ratio of Ni to Co to Mn is 1:1.06;
(2) Monocrystal nickel-enriched ternary anode material LiNi 0.6 Co 0.2 Mn 0.2 O 2 Mixing with tungsten trioxide, placing into a calciner, and introducing into a furnace under argon atmosphere at 5deg.CHeating to 800 ℃ at the heating rate of min, calcining for 2h, and cooling along with a furnace to obtain the tungsten-coated and doped monocrystal nickel-rich ternary anode material;
wherein the tungsten trioxide has the mass of monocrystal nickel-rich ternary anode material LiNi 0.6 Co 0.2 Mn 0.2 O 2 1% of the mass of the mixture with tungsten trioxide.
Example 3
The preparation method of the tungsten coated and/or doped monocrystal nickel-rich ternary positive electrode material aims at the monocrystal nickel-rich ternary positive electrode material, and only one preparation method is used for simultaneously realizing single coating, single doping and both coating and doping modification of the material, and specifically comprises the following steps:
(1) 4.7038g of Ni, co and Mn ternary precursor Ni 0.6 Co 0.2 Mn 0.2 (OH) 2 Mixing with 2.2692g of lithium hydroxide, then placing into a calciner, heating to 950 ℃ at a heating rate of 5 ℃/min under an oxygen atmosphere, calcining for 10 hours, and then placing into a ball mill according to a ball-material ratio of 10:1, ball-milling for 1 hour at a rotating speed of 200r/min to obtain the monocrystal nickel-rich ternary anode material LiNi 0.6 Co 0.2 Mn 0.2 O 2 ；
Wherein, li and Ni-Co-Mn ternary precursor Ni in lithium hydroxide 0.6 Co 0.2 Mn 0.2 (OH) 2 The molar ratio of Ni to Co to Mn is 1:1.06;
(2) Monocrystal nickel-enriched ternary anode material LiNi 0.6 Co 0.2 Mn 0.2 O 2 Mixing with tungsten trioxide, then placing into a calciner, heating to 800 ℃ at a heating rate of 5 ℃/min under argon atmosphere, calcining for 2 hours, and cooling along with the calciner to obtain the tungsten-coated and doped monocrystal nickel-rich ternary anode material;
wherein the tungsten trioxide has the mass of monocrystal nickel-rich ternary anode material LiNi 0.6 Co 0.2 Mn 0.2 O 2 1.5% of the mixture with tungsten trioxide.
Comparative example 1
The difference from example 1 is that "single crystal nickel-rich ternary cathode material LiNi is not included 0.6 Co 0.2 Mn 0.2 O 2 Mixing with tungsten trioxide to obtain the monocrystal nickel-rich ternary anode material.
Performance testing
1. X-ray diffraction (XRD) test
FIG. 1 is an XRD comparison of samples prepared in examples 1-3 and comparative example.
As can be seen from FIG. 1, the samples of comparative example 1 and examples 1-3 are all typical of alpha-NaFeO 2 The structure belongs to the R3m space group, and the samples of examples 1-3 also have no diffraction peaks of other phases detected. Indicating that WO is not detectable except for a small amount thereof 3 The addition of (3) does not alter the bulk structure of the overall phase.
2. Scanning electron microscope test
Fig. 2 is a scanning electron microscope image of the sample prepared in comparative example 1, and fig. 3 is a scanning electron microscope image of the sample prepared in example 2.
From fig. 2 and 3 and from a finish analysis of XRD results, it is understood that the samples of comparative example 1 and example 2 each have a single crystal structure, and the sample of example 2 has a lithium-rich state.
3. High Resolution Transmission Electron Microscope (HRTEM) test and selected area fourier transform results
Fig. 4 is a HRTEM image of a sample and a fourier transform image of a selected region obtained in comparative example 1, fig. 5 is a HRTEM image of a sample and a fourier transform image of a selected region obtained in example 1 (coating), fig. 6 is a HRTEM image of a sample and a fourier transform image of a selected region obtained in example 2 (coating doped lithium-rich layer), and fig. 7 is a HRTEM image of a sample and a fourier transform image of a selected region obtained in example 3 (doping).
As can be seen from fig. 4, the outer surface of the particles of the sample of comparative example 1 forms a salt-rock phase layer. As can be seen from FIGS. 5 to 7, in examples 1 to 3, WO is finely controlled 3 The single cladding, doping, cladding and single doping of the single-crystal nickel-rich ternary material are respectively realized.
4. Cycle and rate performance test
Samples prepared in examples 1 to 3 and comparative example 1 were assembled with a metal lithium sheet and the like, respectively, to form button cells, and their cycle and rate performance were tested at voltage intervals of 2.8 to 4.4V. The results are shown in Table 1 and FIGS. 8-9.
Wherein, FIG. 8 is a cycle performance chart of samples prepared in examples 1-3 and comparative example 1 (corresponding capacity curves at 300 circles are example 2, example 1, example 3 and comparative example 1 in order from top to bottom), and FIG. 9 is a rate performance chart of samples prepared in examples 1-3 and comparative example 1.
TABLE 1 button cell performance test results
As can be seen from table 1 and fig. 8, the tungsten coated and doped single crystal nickel-rich ternary cathode materials prepared in examples 1 to 3 were higher in capacity retention than comparative example 1 after 300 cycles at a current density of 1C in the voltage range of 2.8 to 4.4V. Among them, example 2 is the best example, and the capacity retention rate is improved by 31.2% after 300 cycles compared with comparative example 1.
The test shows that the cycling performance stability of the tungsten coated and doped monocrystal nickel-rich ternary positive electrode material prepared by the method is obviously improved.
As can be seen from fig. 9, the high rate discharge capacities of the samples of examples 1 to 3 were all higher than that of comparative example 1. Among them, example 2 is the best example, the 10C high rate capacity is up to 147.5mAh/g, which is 8.1% higher than the 10C high rate capacity of comparative example 1.
The method has obvious effect and improves the electrochemical performance of the positive electrode material. Wherein, the realization of the elimination of the lithium-rich state of lithium-nickel mixed discharge while cladding doping is shown to be the most excellent electrochemical performance.
The previous description of the disclosed embodiments is provided to enable any person skilled in the art to make or use the present invention. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other embodiments without departing from the spirit or scope of the invention. Thus, the present invention is not intended to be limited to the embodiments shown herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.

Claims (1)

1. The preparation method of the tungsten coated and doped monocrystal nickel-rich ternary cathode material is characterized in that aiming at the monocrystal nickel-rich ternary cathode material, the single coating, single doping and the modification method for coating and doping of the material are realized simultaneously in one preparation method, and the preparation method specifically comprises the following steps:
(1) Mixing the nickel-cobalt-manganese ternary precursor with a lithium source, calcining, and ball milling to obtain a monocrystal nickel-rich ternary positive electrode material;
the chemical formula of the nickel-cobalt-manganese ternary precursor is Ni 0.6 Co 0.2 Mn 0.2 (OH) 2 ；
The lithium source is at least one of lithium hydroxide, lithium carbonate, lithium oxide, lithium chloride, lithium nitrate and lithium oxalate;
the molar ratio of Li in the lithium source to Ni+Co+Mn in the nickel-cobalt-manganese ternary precursor is 1 (1.0-1.1);
the temperature rising rate of the calcination is 2-6 ℃/min, the temperature is 500-1000 ℃, the calcination atmosphere is air and/or oxygen, and the time is 3-15h;
the ball-milling material ratio is 10:1, the rotating speed is 200-500r/min, and the time is 0.5-2h;
the chemical formula of the monocrystal nickel-rich ternary positive electrode material is as follows: li (Li) a Ni x Co y Mn 1-x-y O 2 The method comprises the steps of carrying out a first treatment on the surface of the Wherein x is more than or equal to 0.6 and less than or equal to 1, y is more than or equal to 0.20, z is more than or equal to 0 and less than or equal to 0.20, and x+y+z=1; a is more than or equal to 0.95 and less than or equal to 1.10;
(2) Mixing the monocrystal nickel-rich ternary anode material with a tungsten source, calcining, and cooling to obtain the monocrystal nickel-rich ternary anode material coated and doped with tungsten;
the tungsten source is at least one of tungsten trioxide, lithium tungstate, sodium tungstate and tungstic acid;
the mass of the tungsten source is 0.01% -3% of the mass of the mixture of the monocrystal nickel-rich ternary anode material and the tungsten source;
the temperature rising rate of the calcination is 2-6 ℃/min, the temperature is 400-900 ℃, the calcination atmosphere is argon, and the time is 1-5h.
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